Golf ball composition

ABSTRACT

Disclosed embodiments concern a golf ball comprising a core comprising a center, an outer cover layer, and optionally one or more intermediate layers. One or more of the core, outer cover layer or one or more intermediate layers includes a blend composition including from about 85 to about 99 wt % of a block copolymer and from about 1 to about 15 wt % (based on the final weight of the blend) of one or more modifying agents including amino acids, aminotriazines, dicyandiamides and polyamines and any of their combinations.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of the earlier filing date of U.S.Provisional Application No. 61/291,508, filed on Dec. 31, 2009, which isincorporated herein by reference.

FIELD

The present disclosure relates to sports equipment in general and moreparticularly to golf balls comprising a modified block copolymercomposition. In one embodiment, the presently described modified blockcopolymer composition is used in the manufacture of a golf ballcomprising a core, a cover layer and, optionally, one or more innercover layers. In one embodiment, a golf ball is disclosed in which theouter cover layer comprises the modified block copolymer composition. Inanother embodiment, a golf ball is disclosed in which at least oneintermediate layer comprises the modified block copolymer composition.In another embodiment, a golf ball is disclosed in which the corecomprises the modified block copolymer composition.

DESCRIPTION OF RELATED ART

The application of synthetic polymer chemistry to the field of sportsequipment has revolutionized the performance of athletes in many sports.One sport in which this is particularly true is golf, especially asrelates to advances in golf ball performance and ease of manufacture.For instance, the earliest golf balls consisted of a leather coverfilled with wet feathers. These “feathery” golf balls were subsequentlyreplaced with a single piece golf ball made from “gutta percha,” anaturally occurring rubber-like material. In the early 1900's, the woundrubber ball was introduced, consisting of a solid rubber core aroundwhich rubber thread was tightly wound with a gutta percha cover.

More modern golf balls can be classified as one-piece, two-piece,three-piece or multi-layered golf balls. One-piece balls are molded froma homogeneous mass of material with a dimple pattern molded thereon.One-piece balls are inexpensive and very durable, but do not providegreat distance because of relatively high spin and low velocity.Two-piece balls are made by molding a cover around a solid rubber core.These are the most popular types of balls in use today. In attempts tofurther modify the ball performance especially in terms of the distancesuch balls travel and the feel transmitted to the golfer through theclub on striking the ball, the basic two-piece ball construction hasbeen further modified by the introduction of additional layers betweenthe core and outer cover layer. If one additional layer is introducedbetween the core and outer cover layer a so called “three-piece ball”results and similarly, if two additional layers are introduced betweenthe core and outer cover layer, a so called “four-piece ball” results,and so on.

Modern golf ball covers were previously made from balata rubber, whichwas favored by some players because the softness of the cover allowsthem to achieve spin rates sufficient to allow more precisely control ofball direction and distance, particularly on shorter approach shots.However balata-covered balls, although exhibiting high spin and softfeel, were often deficient in terms of the velocity of the ball when itleaves the club face which in turn affects the distance the balltravels. This distance is directly related to the coefficient ofrestitution (“C.O.R.”) of the ball. In a multi-layered golf ball, thecoefficient of restitution is a function of the properties of the core,the cover and any additional layer. While there are no United StatesGolf Association (“USGA”) limitations on the coefficient of restitutionvalues of a golf ball, the USGA requires that the golf ball cannotexceed an initial velocity of 255 feet/second. As a result, golf ballmanufacturers generally seek to maximize the coefficient of restitutionof a ball without exceeding the velocity limitation.

Accordingly, a variety of golf ball constructions have been developed inan attempt to provide spin rates and a feel approaching those of balatacovered balls, while also providing a golf ball with a higher durabilityand overall distance. This has resulted in the emergence of balls, whichhave a solid rubber core, a cover, and one, or more so calledintermediate layers, as well as the application of new materials to eachof these components.

One elastomeric material that provides for good performance when used inmaking ball cores, outer covers and intermediate layers is a blockcopolymer, especially those having a first polymer block comprising anaromatic vinyl compound, and a second polymer block comprising a dienecompound. Such block copolymers can be used as the single component of acore, cover or intermediate layer but can also be used as a blendcomponent with other polymers to yield the desired performanceproperties. However, it has been observed that layers incorporatingthese block copolymers can suffer from cracks after being hit duringplay. During endurance testing of balls having covers incorporatingblock copolymers, crack initiation and propagation was observed in thecovers. This cracking leads to substantial deterioration in ballperformance and long-term durability. These cracks also can initiate inan intermediate layer and subsequently propagate to a cover.Additionally, shear-cut resistance in the covers needs to be furtherimproved for optimal performance.

SUMMARY

In view of the above, it is apparent that golf ball cover andintermediate layers are needed that allow the optimization of golf ballperformance properties by incorporating block copolymers into thelayers, while eliminating or reducing formation of cracks in the coversand intermediate layers and improving the shear resistance of thelayers. The ball layers also should provide little or no processing andpreparation difficulties beyond that provided by present layers. We havenow surprisingly found that the durability of such block copolymerseither in a single composition or in their blend compositions can beimproved by adding selected modifiers, including amino acids,aminotriazines, dicyandiamides and polyamines, to form a modified blockcopolymer composition (“MBC”).

An especially preferred modifier used to form the MBC is a compoundhaving the general formula:

(R₂N)_(m)—R′—(X(O)_(n)(OR)_(y))_(m),

where R is hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromaticgroup; R′ is a bridging group comprising one or more C₁-C₂₀ straightchain or branched aliphatic or alicyclic groups, or substituted straightchain or branched aliphatic or alicyclic groups, or aromatic groups, oran oligomer of up to 12 repeating units including, but not limited to,polypeptides derived from an amino acid sequence of up to 12 aminoacids; and X is C or S or P with the proviso that when X=C, n=1 and y=1and when X=S, n=2 and y=1, and when X=P, n=0-1 and y=2 or 4, and m=1-3.

Certain disclosed embodiments of the present invention concern a golfball having a core comprising a center; an outer cover layer; andoptionally one or more intermediate layers; and where one or more of thecore, outer cover layer or one or more intermediate layers includes ablend composition which includes from about 85 to about 99 wt % of ablock copolymer and from about 1 to about 15 wt % (based on the finalweight of the blend) of one or more modifying agents selected from thegroup consisting of amino acids, aminotriazines, dicyandiamides andpolyamines; either alone or in combination.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates a three-piece golf ball 1 comprising a solid centeror core 2, an intermediate layer 3, and an outer cover layer 4.

FIG. 2 illustrates a 4-piece golf ball 1 comprising a core 2, and anouter cover layer 5, an inner intermediate layer 3, and an outerintermediate layer 4.

Although FIGS. 1 and 2 illustrate only three- and four-piece golf ballconstructions, golf balls of the present invention may comprise from 1to at least 5 intermediate layer(s), preferably from 1 to 3 intermediatelayer(s), more preferably from 1 to 2 intermediate layer(s).

DETAILED DESCRIPTION I. Definitions

Any numerical values recited herein include all values from the lowervalue to the upper value in increments of one unit provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent or a value of a process variable is from 1 to 90, preferablyfrom 20 to 80, more preferably from 30 to 70, it is intended that valuessuch as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expresslyenumerated in this specification. For values, which have less than oneunit difference, one unit is considered to be 0.1, 0.01, 0.001, or0.0001 as appropriate. Thus all possible combinations of numericalvalues between the lowest value and the highest value enumerated hereinare said to be expressly stated in this application.

The term “aliphatic” is intended to mean any open or closed chainmolecule, excluding aromatic compounds, containing only carbon andhydrogen atoms which are joined by single bonds (alkanes), double bonds(alkenes), or triple bonds (alkynes). This term encompasses substitutedaliphatic compounds, saturated aliphatic compounds, and unsaturatedaliphatic compounds.

The terms “aromatic” and “aryl” refer to a substantiallyhydrocarbon-based aromatic compound, or a radical thereof (e.g. C6H5) asa substituent bonded to another group, particularly other organicgroups, having a ring structure as exemplified by benzene, naphthalene,phenanthrene, anthracene, etc.

The terms “alicyclic” and “cycloaliphatic” refer to aliphatic compoundswherein carbon atoms are connected in a ring instead of a chain.

The term “(meth)acrylic acid copolymers” is intended to mean copolymersof methacrylic acid and/or acrylic acid.

The term “(meth)acrylate” is intended to mean an ester of methacrylicacid and/or acrylic acid.

The term “partially neutralized” is intended to mean an ionomer with adegree of neutralization of the acid groups in the polymer of less than100 percent.

The term “hydrocarbyl” is intended to mean any aliphatic,cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substitutedcycloaliphatic, aliphatic substituted aromatic, or cycloaliphaticsubstituted aromatic groups. The aliphatic or cycloaliphatic groups arepreferably saturated. Likewise, the term “hydrocarbyloxy” means ahydrocarbyl group having an oxygen linkage between it and the carbonatom to which it is attached.

As used herein, a “blend composition” can be a physical mixture of theindividual components and/or a reaction product produced by a reactionbetween one or more of the individual components.

As used herein, the term “block copolymer” is intended to mean a polymercomprising two or more homopolymer subunits linked by covalent bonds.The union of the homopolymer subunits may require an intermediatenon-repeating subunit, known as a junction block. Block copolymers withtwo or three distinct blocks are called diblock copolymers and triblockcopolymers, respectively.

As used herein, the term “core” is intended to mean the elastic centerof a golf ball. The core may have one or more “core layers” of elasticmaterial, which are usually made of rubbery material such as dienerubbers.

The term “cover layer” is intended to mean the outermost layer of thegolf ball; this is the layer that is directly in contact with paintand/or ink on the surface of the golf ball. If the cover consists of twoor more layers, only the outermost layer is designated the cover layer,and the remaining layers (excluding the outermost layer) are commonlydesignated intermediate layers as herein defined. The term “outer coverlayer” as used herein is used interchangeably with the term “coverlayer.”

The term “intermediate layer” may be used interchangeably herein withthe terms “mantle layer” or “inner cover layer” and is intended to meanany layer(s) in a golf ball disposed between the core and the outercover layer. Should a ball have more than one intermediate layer, thesemay be distinguished as “inner intermediate” or “inner mantle” layerswhich are used interchangeably to refer to the intermediate layer nearerthe core and further from the outer cover, as opposed to the “outerintermediate” or “outer mantle layer” which are also usedinterchangeably to refer to the intermediate layer further from the coreand closer to the outer cover.

The term “prepolymer” as used herein is intended to mean any materialthat can be further processed to form a final polymer material of amanufactured golf ball, such as, by way of example and not limitation, apolymerized or partially polymerized material that can undergoadditional processing, such as crosslinking.

A “thermoplastic” as used herein is intended to mean a material that iscapable of softening or melting when heated and of hardening again whencooled. Thermoplastic polymer chains often are not cross-linked or arelightly crosslinked using a chain extender, but the term “thermoplastic”as used herein may refer to materials that initially act asthermoplastics, such as during an initial extrusion process or injectionmolding process, but which also may be crosslinked, such as during acompression molding step to form a final structure.

A “thermoset” as used herein is intended to mean a material thatcrosslinks or cures via interaction with as crosslinking or curingagent. Crosslinking may be induced by energy, such as heat (generallyabove 200° C.), through a chemical reaction (by reaction with a curingagent), or by irradiation. The resulting composition remains rigid whenset, and does not soften with heating. Thermosets have this propertybecause the long-chain polymer molecules cross-link with each other togive a rigid structure. A thermoset material cannot be melted andre-molded after it is cured. Thus thermosets do not lend themselves torecycling unlike thermoplastics, which can be melted and re-molded.

The term “thermoplastic polyurethane” as used herein is intended to meana material prepared by reaction of a prepared by reaction of adiisocyanate with a polyol, and optionally addition of a chain extender.

The term “thermoplastic polyurea” as used herein is intended to mean amaterial prepared by reaction of a prepared by reaction of adiisocyanate with a polyamine, with optionally addition of a chainextender.

The term “thermoset polyurethane” as used herein is intended to mean amaterial prepared by reaction of a diisocyanate with a polyol, and acuring agent.

The term “thermoset polyurea” as used herein is intended to mean amaterial prepared by reaction of a diisocyanate with a polyamine, and acuring agent.

A “urethane prepolymer” as used herein is intended to mean the reactionproduct of diisocyanate and a polyol.

A “urea prepolymer” as used herein is intended to mean the reactionproduct of a diisocyanate and a polyamine.

The term “zwitterion” as used herein is intended to mean a form of thecompound having both a positively charged species or functional groupand a negatively charged species or functional group, such as an aminegroup and carboxylic acid group, Component (B), where both are chargedand where the net charge on the compound is neutral.

The term “bimodal polymer” refers to a polymer comprising two mainfractions and more specifically to the form of the polymers molecularweight distribution curve, i.e., the appearance of the graph of thepolymer weight fraction as function of its molecular weight. When themolecular weight distribution curves from these fractions aresuperimposed into the molecular weight distribution curve for the totalresulting polymer product, that curve will show two maxima or at leastbe distinctly broadened in comparison with the curves for the individualfractions. Such a polymer product is called bimodal. It is to be notedhere that also the chemical compositions of the two fractions may bedifferent.

Similarly the term “unimodal polymer” refers to a polymer comprising onemain fraction and more specifically to the form of the polymersmolecular weight distribution curve, i.e., the molecular weightdistribution curve for the total polymer product shows only a singlemaximum.

The term “sports equipment” refers to any item of sports equipments suchas sports clothing, boots, sneakers, clogs, sandals, slip on sandals andshoes, golf shoes, tennis shoes, running shoes, athletic shoes, hikingshoes, skis, ski masks, ski boots, cycling shoes, soccer boots, golfclubs, golf bags, and the like.

The present invention can be used in forming golf balls of any desiredsize. “The Rules of Golf” by the USGA dictate that the size of acompetition golf ball must be at least 1.680 inches in diameter;however, golf balls of any size can be used for leisure golf play. Thepreferred diameter of the golf balls is from about 1.680 inches to about1.800 inches. The more preferred diameter is from about 1.680 inches toabout 1.760 inches. A diameter of from about 1.680 inches to about 1.740inches is most preferred; however diameters anywhere in the range offrom 1.70 to about 2.0 inches can be used. Oversize golf balls withdiameters above about 1.760 inches to as big as 2.75 inches are alsowithin the scope of the invention.

II. Block Copolymer

The compositions used to make the golf balls of the present inventionare the block copolymers including di- and triblock copolymers,incorporating (a) a first polymer block having an aromatic vinylcompound, and (b) a second polymer block having an olefinic and/orconjugated diene compound. Preferred aromatic vinyl compounds includestyrene, α-methylstyrene, o-, m- or p-methylstyrene, 4-propylstyrene,1,3-dimethylstyrene, vinylnaphthalene and vinylanthracene. Inparticular, styrene and α-methylstyrene are preferred. These aromaticvinyl compounds can each be used alone, or can be used in combination oftwo or more kinds. The aromatic vinyl compound is preferably containedin the block copolymer A in an amount of from 5 to 75% by weight, andmore preferably from 10 to 65% by weight.

The conjugated diene compound, that constitutes the polymer block (b) inthe block copolymer includes, but is not limited to 1,3-butadiene,isoprene, 2,3-diemthyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene.In particular, isoprene and 1,3-butadiene are preferred. Illustrativeolefinic compounds include ethylene, propylene, and butene. Theseconjugated olefinic or diene compounds can each be used alone, or can beused in combination of two or more kinds.

Examples of such block copolymers include styrenic block copolymersincluding styrene-butadiene-styrene (SBS), styrene-isoprene-styrene(SIS), styrene-ethylene-butylene-styrene, (SEBS) andstyrene-ethylene/propylene-styrene (SEPS). Also included arefunctionalized styrenic block copolymers, including those where theblock copolymer incorporates a first polymer block having an aromaticvinyl compound, a second polymer block having a conjugated dienecompound and a hydroxyl group located at a block copolymers. Alsoincluded are the hydrogenation products of these block copolymers. Apreferred functionalized styrenic block copolymer is SEPTON HG-252. Suchblock copolymers are described in more detail in commonly-assigned U.S.Pat. No. 6,861,474 and U.S. Patent Publication No. 2003/0224871, both ofwhich are incorporated herein by reference in their entireties.

Commercial examples include SEPTON marketed by Kuraray Company ofKurashiki, Japan; TOPRENE by Kumho Petrochemical Co., Ltd and KRATONmarketed by Kraton Polymers.

III. Amino Acid Modifier

The block copolymers are mixed with modifying agents including aminoacids having both amine and acid functionality. One such modifying agentis a compound having the general formula:

(R₂N)_(m)—R′—(X(O)_(n)(OR)_(y))_(m),

where R is hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromaticgroup; R′ is a bridging group comprising one or more C₁-C₂₀ straightchain or branched aliphatic or alicyclic groups, substituted straightchain or branched aliphatic or alicyclic groups, aromatic groups, or anoligomer of up to 12 repeating units including, but not limited to,polypeptides derived from an amino acid sequence of up to 12 aminoacids; and X is C or S or P with the proviso that when X=C, n=1 and y=1and when X=S, n=2 and y=1, and when X=P, n=0-1 and y=2 or 4, and m=1-3.These materials are more fully described in copending U.S. patentapplication Ser. No. 11/182,170, filed on Jul. 14, 2005, the entirecontents of which are incorporated herein by reference.

Preferred examples include, but are not limited to, 11-aminoundecanoicacid, and 12-aminododecanoic acid. Also included as modifiers are4,4′-methylene-bis-(cyclohexylamine)-carbamate (commercially availablefrom R.T. Vanderbilt Co., Norwalk, Conn. under the tradename Diak® 4),epsilon-caprolactam; omega-caprolactam, and any and all combinationsthereof.

IV. Aminotriazine Modifier

Another amine-functionalized modifying agent for the block copolymersare the aminotriazines, as disclosed in copending U.S. application Ser.No. 12/424,401, filed on Apr. 15, 2009, and now published as US2009/0270201 A1, the entire contents of which are incorporated herein byreference.

These aminotriazenes have the general formula;

where R₁-R₅ are independently aliphatic, substituted aliphatic, alkoxy,amine, aryl, substituted aryl, heteroaryl, substituted heteroarylgroups, hydrogen or halogen. Preferred examples include but are notlimited to guanamine, 6-methyl-1,3,5-triazine-2,4-diamine(acetoguanamine), 6-nonyl-1,3,5-triazine-2,4-diamine (nonylguanamine),6-phenyl-1,3,5-triazine-2,4-diamine (benzoguanamine), or2,4,6-triamino-triazine (melamine).

V. Dicyandiamide Modifier

Another amine-functionalized modifying agent for the block copolymersinclude the family of dicyandiamides as described in copendingapplication Ser. No. 11/809,432 filed on May 31, 2007, by Kim et al.,the entire contents of which are hereby incorporated by reference. Thedicyandiamides used in the present invention have the general formula:

where R and R′ independently are hydrogen, or a C₁-C₂₀ aliphatic,cycloaliphatic or aromatic moiety or substituted aliphatic,cycloaliphatic or aromatic moiety. For example R may be H, —CH₃, —C₂H₅,—C₆H₅, —CH₂X, —C₂H₄X, —C₆H₄X, —CH₂C₆H₄X, —CH₂CH₂C₆H₄X, or any and allcombinations thereof, and where X may be hydrogen, a methyl group, anethyl group, a methoxy group, an ethoxy group, an amino group and adimethylamino group or any and all combinations thereof. Examplesinclude but are not limited to 2-Cyanoguanidine, N-benzyldicyandiamide,N-(4-methylbenzyl)dicyandiamide, N-(4-methoxybenzyl)dicyandiamide,N-phenethyldicyandiamide; N-(4-methylphenethyl)dicyandiamide; andN-(4-methoxyphenethyl)dicyandiamide. Also included are the dicyandiamidederivatives disclosed in U.S. Pat. No. 5,620,831 by Osamu Kewana issuingon 15 April, 1997, the entire contents of which are herein incorporatedby reference.

A preferred dicyandiamide is 2-Cyanoguanidine which may be commerciallyacquired from Degussa AG under the trade name Dyhard®.

VI. Polyamines

Another amine-functionalized modifying agent for the block copolymersare the various polyamines. These include primary, secondary andtertiary amines having two or more amines as functional groups.Exemplary diamines include aliphatic diamines, such astetramethylenediamine, pentamethylenediamine, hexamethylenediamine;alicyclic diamines, such as 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane, bis(1,3-aminomethyl)cyclohexane (BAC); or aromatic diamines,such asdiethyl-2,4-toluenediamine-4,4″-methylenebis-(3-chloro,2,6-diethyl)-aniline(available from Air Products and Chemicals Inc., of Allentown, Pa.,under the trade name LONZACURE®), 3,3′-dichlorobenzidene;3,3′-dichloro-4,4′-diaminodiphenyl methane (MOCA);N,N,N′,N′-tetrakis(2-hydroxypropyl)-ethylenediamine,3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; N,N′-dialkyldiamino diphenylmethane; trimethylene-glycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate, 4,4′-methylenebis-2-chloroaniline, 2,2′,3,3′-tetrachloro-4,4′-diamino-phenyl methane,p,p′-methylenedianiline, p-phenylenediamine or 4,4′-diaminodiphenyl; and2,4,6-tris(dimethylaminomethyl)phenol. An especially preferred diamineis bis(1,3-aminomethyl)cyclohexane (BAC).

The MBC composition preferably is prepared by mixing the above materialsinto each other thoroughly, either by using a dispersive mixingmechanism, a distributive mixing mechanism, or a combination of these.These mixing methods are well known in the manufacture of polymerblends.

The resulting MBC compositions may be further modified by the additionof an impact modifier, which can include copolymers or terpolymershaving a glycidyl group, hydroxyl group, maleic anhydride group orcarboxylic group, collectively referred to as functionalized polymers.These copolymers and terpolymers may comprise an α-olefin. Examples ofsuitable α-olefins include ethylene, propylene, 1-butene, 1-pentene,3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,1-octene, 1-decene-, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene,1-octacocene, and 1-triacontene. One or more of these α-olefins may beused.

VII. Additional Polymer Components

Other polymeric materials generally considered useful for making golfballs may also be included as a blend component with MBC or as aseparate component of the core or one or more layers of the golf ballsof the present invention. These include, without limitation, syntheticand natural rubbers, thermoset polymers such as other thermosetpolyurethanes or thermoset polyureas, as well as thermoplastic polymersincluding thermoplastic elastomers such as metallocene catalyzedpolymer, unimodal ethylene/carboxylic acid copolymers, unimodalethylene/carboxylic acid/carboxylate terpolymers, bimodalethylene/carboxylic acid copolymers, bimodal ethylene/carboxylicacid/carboxylate terpolymers, thermoplastic polyurethanes, thermoplasticpolyureas, polyamides, copolyamides, polyesters, copolyesters,polycarbonates, polyolefins, halogenated (e.g. chlorinated) polyolefins,halogenated polyalkylene compounds, such as halogenated polyethylene[e.g. chlorinated polyethylene (CPE)], polyalkenamer, polyphenyleneoxides, polyphenylene sulfides, diallyl phthalate polymers, polyimides,polyvinyl chlorides, polyamide-ionomers, polyurethane-ionomers,polyvinyl alcohols, polyarylates, polyacrylates, polyphenylene ethers,impact-modified polyphenylene ethers, polystyrenes, high impactpolystyrenes, acrylonitrile-butadiene-styrene copolymers,styrene-acrylonitriles (SAN), acrylonitrile-styrene-acrylonitriles,styrene-maleic anhydride (S/MA) polymers, styrenic block copolymersincluding styrene-butadiene-styrene (SBS),styrene-ethylene-butylene-styrene, (SEBS) andstyrene-ethylene-propylene-styrene (SEPS), styrenic terpolymers,functionalized styrenic block copolymers including hydroxylated,functionalized styrenic copolymers, and terpolymers, cellulosicpolymers, liquid crystal polymers (LCP), ethylene-propylene-dieneterpolymers (EPDM), ethylene-vinyl acetate copolymers (EVA),ethylene-propylene copolymers, propylene elastomers (such as thosedescribed in U.S. Pat. No. 6,525,157, to Kim et al., the entire contentsof which is hereby incorporated by reference in its entirety), ethylenevinyl acetates, polyureas, and polysiloxanes and any and allcombinations thereof.

One preferred polymer for blending with the modified block copolymerand/or used as a separate component of the core or one or more layers ofthe golf balls of the present invention are the olefin/unsaturated acidcontaining polymers including the ethylene/(meth)acrylic acid copolymersand ethylene/(meth)acrylic acid/alkyl(meth)acrylate terpolymers, orethylene and/or propylene maleic anhydride copolymers and terpolymers.Examples of such polymers which are commercially available include, butare not limited to, the Escor® 5000, 5001, 5020, 5050, 5070, 5100, 5110and 5200 series of ethylene-acrylic acid copolymers sold by Exxon andthe Primacor® 1321, 1410, 1410-XT, 1420, 1430, 2912, 3150, 3330, 3340,3440, 3460, 4311, 4608 and 5980 series of ethylene-acrylic acidcopolymers sold by The Dow Chemical Company, Midland, Mich. and theethylene-acrylic acid copolymers Nucrel 599, 699, 0903, 0910, 925, 960,2806, and 2906 ethylene-methacrylic acid copolymers. sold by DuPont Alsoincluded are the bimodal ethylene/carboxylic acid polymers as describedin U.S. Pat. No. 6,562,906, the contents of which are incorporatedherein by reference. These polymers comprise ethylene/α,β-ethylenicallyunsaturated C₃₋₈ carboxylic acid high copolymers, particularly ethylene(meth)acrylic acid copolymers and ethylene, alkyl(meth)acrylate,(meth)acrylic acid terpolymers, having molecular weights of about 80,000to about 500,000 which are melt blended with ethylene/α,β-ethylenicallyunsaturated C₃₋₈ carboxylic acid copolymers, particularlyethylene/(meth)acrylic acid copolymers having molecular weights of about2,000 to about 30,000.

Another preferred polymer for blending with the modified block copolymerand/or used as a separate component of the core or one or more layers ofthe golf balls of the present invention is an ionomer resin. One familyof such resins was developed in the mid-1960's, by E.I. DuPont deNemours and Co., and is sold under the trademark SURLYN®. Preparation ofsuch ionomers is well known, for example see U.S. Pat. No. 3,264,272,which is incorporated herein by reference. Generally speaking, mostcommercial ionomers are unimodal and consist of a polymer of amono-olefin, e.g., an alkene, with an unsaturated mono- or dicarboxylicacids having 3 to 12 carbon atoms. An additional monomer in the form ofa mono- or dicarboxylic acid ester may also be incorporated in theformulation as a so-called “softening comonomer”. The incorporatedcarboxylic acid groups are then neutralized by a basic metal ion salt,to form the ionomer. The metal cations of the basic metal ion salt usedfor neutralization include Li⁺, Na⁺, K⁺, Zn²⁺, Ca²⁺, Co²⁺, Ni²⁺, Cu²⁺,Pb²⁺, and Mg²⁺, with the Li⁺, Na⁺, Ca²⁺, Zn²⁺, and Mg²⁺ being preferred.The basic metal ion salts include those of for example formic acid,acetic acid, nitric acid, and carbonic acid, hydrogen carbonate salts,oxides, hydroxides, and alkoxides.

The first commercially available ionomer resins contained up to 16weight percent acrylic or methacrylic acid, although it was also wellknown at that time that, as a general rule, the hardness of these covermaterials could be increased with increasing acid content. Hence, inResearch Disclosure 29703, published in January 1989, DuPont disclosedionomers based on ethylene/acrylic acid or ethylene/methacrylic acidcontaining acid contents of greater than 15 weight percent. In this samedisclosure, DuPont also taught that such so called “high acid ionomers”had significantly improved stiffness and hardness and thus could beadvantageously used in golf ball construction, when used either singlyor in a blend with other ionomers.

More recently, high acid ionomers can be ionomer resins with acrylic ormethacrylic acid units present from 16 wt. % to about 35 wt. % in thepolymer. Generally, such a high acid ionomer will have a flexuralmodulus from about 50,000 psi to about 125,000 psi.

Ionomer resins further comprising a softening comonomer, present fromabout 10 wt. % to about 50 wt. % in the polymer, have a flexural modulusfrom about 2,000 psi to about 10,000 psi, and are sometimes referred toas “soft” or “very low modulus” ionomers. Typical softening comonomersinclude n-butyl acrylate, iso-butyl acrylate, n-butyl methacrylate,methyl acrylate and methyl methacrylate.

Today, there are a wide variety of commercially available ionomer resinsbased both on copolymers of ethylene and (meth)acrylic acid orterpolymers of ethylene and (meth)acrylic acid and (meth)acrylate, allof which many of which are be used as a golf ball component. Theproperties of these ionomer resins can vary widely due to variations inacid content, softening comonomer content, the degree of neutralization,and the type of metal ion used in the neutralization. The full rangecommercially available typically includes ionomers of polymers ofgeneral formula, E/X/Y polymer, wherein E is ethylene, X is a C₃ to C₈α, β ethylenically unsaturated carboxylic acid, such as acrylic ormethacrylic acid, and is present in an amount from about 2 to about 30weight % of the E/X/Y copolymer, and Y is a softening comonomer selectedfrom the group consisting of alkyl acrylate and alkyl methacrylate, suchas methyl acrylate or methyl methacrylate, and wherein the alkyl groupshave from 1-8 carbon atoms, Y is in the range of 0 to about 50 weight %of the E/X/Y copolymer, and wherein the acid groups present in saidionomeric polymer are partially neutralized with basic salts comprisinga metal ion selected from the group consisting of lithium, sodium,potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, or acombination of such cations.

The ionomer may also be a so-called bimodal ionomer as described in U.S.Pat. No. 6,562,906 (the entire contents of which are herein incorporatedby reference). These ionomers are bimodal as they are prepared fromblends comprising polymers of different molecular weights. Specificallythey include bimodal polymer blend compositions comprising:

-   -   a) a high molecular weight component having a weight average        molecular weight, Mw, of about 80,000 to about 500,000 and        comprising one or more ethylene/α,β-ethylenically unsaturated        C₃₋₈ carboxylic acid copolymers and/or one or more ethylene,        alkyl(meth)acrylate, (meth)acrylic acid terpolymers; said high        molecular weight component being partially neutralized with        basic salts comprising metal ions selected from the group        consisting of lithium, sodium, zinc, calcium, magnesium, and a        mixture of any these; and    -   b) a low molecular weight component having a weight average        molecular weight, Mw, of about from about 2,000 to about 30,000        and comprising one or more ethylene/α,β-ethylenically        unsaturated C₃₋₈ carboxylic acid copolymers and/or one or more        ethylene, alkyl(meth)acrylate, (meth)acrylic acid terpolymers;        said low molecular weight component being partially neutralized        with basic salts comprising metal ions selected from the group        consisting of lithium, sodium, potassium, magnesium, calcium,        barium, lead, tin, zinc or aluminum, and a mixture of any these.

In addition to the unimodal and bimodal ionomers, also included are theso-called “modified ionomers” examples of which are described in U.S.Pat. Nos. 6,100,321, 6,329,458 and 6,616,552 and U.S. Patent PublicationUS 2003/0158312 A1, the entire contents of all of which are hereinincorporated by reference.

The modified unimodal ionomers may be prepared by mixing:

-   -   a) an ionomeric polymer comprising ethylene, from 5 to 25 weight        percent (meth)acrylic acid, and from 0, typically greater than 0        to 40 weight percent of a (meth)acrylate monomer, said ionomeric        polymer neutralized with basic salts comprising metal ions        selected from the group consisting of lithium, sodium,        potassium, magnesium, calcium, barium, lead, tin, zinc or        aluminum, and any and all mixtures thereof; and    -   b) from about 5 to about 40 weight percent (based on the total        weight of said modified ionomeric polymer) of one or more fatty        acids or metal salts of said fatty acid, the metal selected from        the group consisting of lithium, sodium, potassium, magnesium,        calcium, barium, lead, tin, zinc or aluminum, and any and all        mixtures thereof; and the fatty acid preferably being stearic        acid.

The modified bimodal ionomers, which are ionomers derived from theearlier described bimodal ethylene/carboxylic acid polymers (asdescribed in U.S. Pat. No. 6,562,906, the entire contents of which areherein incorporated by reference), are prepared by mixing:

-   -   a) a high molecular weight component having a weight average        molecular weight, Mw, of about 80,000 to about 500,000 and        comprising one or more ethylene/α,β-ethylenically unsaturated        C₃₋₈ carboxylic acid copolymers and/or one or more ethylene,        alkyl(meth)acrylate, (meth)acrylic acid terpolymers; said high        molecular weight component being partially neutralized with        basic salts comprising metal ions selected from the group        consisting of lithium, sodium, potassium, magnesium, calcium,        barium, lead, tin, zinc or aluminum, and any and all mixtures        thereof; and    -   b) a low molecular weight component having a weight average        molecular weight, Mw, of about from about 2,000 to about 30,000        and comprising one or more ethylene/α,β-ethylenically        unsaturated C₃₋₈ carboxylic acid copolymers and/or one or more        ethylene, alkyl(meth)acrylate, (meth)acrylic acid terpolymers;        said low molecular weight component being partially neutralized        with basic metal salts comprising metal ions selected from the        group consisting of lithium, sodium, potassium, magnesium,        calcium, barium, lead, tin, zinc or aluminum, and any and all        mixtures thereof; and    -   c) from about 5 to about 40 weight percent (based on the total        weight of said modified ionomeric polymer) of one or more fatty        acids or metal salts of said fatty acid, the metal selected from        the group consisting of lithium, sodium, potassium, magnesium,        calcium, barium, lead, tin, zinc or aluminum, and any and all        mixtures thereof; and the fatty acid preferably being stearic        acid.

The fatty or waxy acid salts utilized in the various modified ionomersare composed of a chain of alkyl groups containing from about 4 to 75carbon atoms (usually even numbered) and characterized by a —COOHterminal group. The generic formula for all fatty and waxy acids aboveacetic acid is CH₃(CH₂)_(X)COOH, wherein the carbon atom count includesthe carboxyl group (i.e. x=2-73). The fatty or waxy acids utilized toproduce the fatty or waxy acid salts modifiers may be saturated orunsaturated, and they may be present in solid, semi-solid or liquidform.

Examples of suitable saturated fatty acids, i.e., fatty acids in whichthe carbon atoms of the alkyl chain are connected by single bonds,include but are not limited to stearic acid (C₁₈, i.e., CH₃(CH₂)₁₆COOH),palmitic acid (C₁₆, i.e., CH₃(CH₂)₁₄COOH), pelargonic acid (C₉, i.e.,CH₃(CH₂)₇COOH) and lauric acid (C₁₂, i.e., CH₃(CH₂)₁₀OCOOH). Examples ofsuitable unsaturated fatty acids, i.e., a fatty acid in which there areone or more double bonds between the carbon atoms in the alkyl chain,include but are not limited to oleic acid (C₁₃, i.e.,CH₃(CH₂)₇CH:CH(CH₂)₇COOH).

The source of the metal ions used to produce the metal salts of thefatty or waxy acid salts used in the various modified ionomers aregenerally various metal salts which provide the metal ions capable ofneutralizing, to various extents, the carboxylic acid groups of thefatty acids. These include the sulfate, carbonate, acetate andhydroxylate salts of zinc, barium, calcium and magnesium.

Since the fatty acid salts modifiers comprise various combinations offatty acids neutralized with a large number of different metal ions,several different types of fatty acid salts may be utilized in theinvention, including metal stearates, laureates, oleates, andpalmitates, with calcium, zinc, sodium, lithium, potassium and magnesiumstearate being preferred, and calcium and sodium stearate being mostpreferred.

The fatty or waxy acid or metal salt of said fatty or waxy acid ispresent in the modified ionomeric polymers in an amount of from about 5to about 40, preferably from about 7 to about 35, more preferably fromabout 8 to about 20 weight percent (based on the total weight of saidmodified ionomeric polymer).

As a result of the addition of the one or more metal salts of a fatty orwaxy acid, from about 40 to 100, preferably from about 50 to 100, morepreferably from about 70 to 100 percent of the acidic groups in thefinal modified ionomeric polymer composition are neutralized by a metalion.

An example of such a modified ionomer polymer is DuPont® HPF-1000available from E. I. DuPont de Nemours and Co. Inc.

Another preferred polymer for blending with the modified block copolymerand/or used as a separate component of the core, outer cover layer orintermediate layer(s) of the golf balls of the present invention are thepolyalkenamers which may be prepared by ring opening metathesispolymerization of one or more cycloalkenes in the presence oforganometallic catalysts as described in U.S. Pat. Nos. 3,492,245, and3,804,803, the entire contents of both of which are herein incorporatedby reference. Examples of suitable polyalkenamer rubbers arepolybutenamer rubber, polypentenamer rubber, polyhexenamer rubber,polyheptenamer rubber, polyoctenamer rubber, polynonenamer rubber,polydecenamer rubber polyundecenamer rubber, polydodecenamer rubber,polytridecenamer rubber. For further details concerning polyalkenamerrubber, see Rubber Chem. & Tech., Vol. 47, page 511-596, 1974, which isincorporated herein by reference.

The polyalkenamer rubber preferably contains from about 50 to about 99,preferably from about 60 to about 99, more preferably from about 65 toabout 99, even more preferably from about 70 to about 90 percent of itsdouble bonds in the trans-configuration. The preferred form of thepolyalkenamer has a trans content of approximately 80%, however,compounds having other ratios of the cis- and trans-isomeric forms ofthe polyalkenamer can also be obtained by blending available productsfor use in making the composition.

The polyalkenamer rubber has a molecular weight (as measured by GPC)from about 10,000 to about 300,000, preferably from about 20,000 toabout 250,000, more preferably from about 30,000 to about 200,000, evenmore preferably from about 50,000 to about 150,000.

The polyalkenamer rubber has a degree of crystallization (as measured byDSC secondary fusion) from about 5 to about 70, preferably from about 6to about 50, more preferably from about from 6.5 to about 50%, even morepreferably from about from 7 to about 45%,

A most preferable polyalkenamer rubber for use in the golf balls of thepresent invention is a polyoctenamer. Polyoctenamer rubbers arecommercially available from Huls AG of Marl, Germany, and through itsdistributor in the U.S., Creanova Inc. of Somerset, N.J., and sold underthe trademark VESTENAMER®. Two grades of the VESTENAMER®trans-polyoctenamer are commercially available: VESTENAMER 8012designates a material having a trans-content of approximately 80% (and acis-content of 20%) with a melting point of approximately 54° C.; andVESTENAMER 6213 designates a material having a trans-content ofapproximately 60% (cis-content of 40%) with a melting point ofapproximately 30° C. Both of these polymers have a double bond at everyeighth carbon atom in the ring.

The polyalkenamer rubbers may also be blended within other polymers andan especially preferred blend is that of a polyalkenamer and apolyamide. A more complete description of the polyalkenamer rubbers aredisclosed in U.S. Pat. No. 7,528,196 and copending U.S. application Ser.No. 12/415,522, filed on Mar. 31, 2009, both in the name of Hyun Kim etal., the entire contents of both of which are hereby incorporated byreference.

Another preferred polymer composition for blending with the modifiedblock copolymer and/or used as a separate component of the core, outercover layer or intermediate layer(s) of the golf balls of the presentinvention is a blend of a homopolyamide or copolyamide which is itselfmodified with a functional polymer modifier. Illustrative polyamides foruse in the polyamide compositions include those obtained by: (1)polycondensation of (a) a dicarboxylic acid, such as oxalic acid, adipicacid, sebacic acid, terephthalic acid, isophthalic acid, or1,4-cyclohexanedicarboxylic acid, with (b) a diamine, such asethylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine orm-xylylenediamine; (2) a ring-opening polymerization of cyclic lactam,such as ε-caprolactam or ω-laurolactam; (3) polycondensation of anaminocarboxylic acid, such as 6-aminocaproic acid, 9-aminononanoic acid,11-aminoundecanoic acid or 12-aminododecanoic acid; (4) copolymerizationof a cyclic lactam with a dicarboxylic acid and a diamine; or anycombination of (1)-(4). In certain examples, the dicarboxylic acid maybe an aromatic dicarboxylic acid or a cycloaliphatic dicarboxylic acid.In certain examples, the diamine may be an aromatic diamine or acycloaliphatic diamine. Specific examples of suitable polyamides includepolyamide 6; polyamide 11; polyamide 12; polyamide 4,6; polyamide 6,6;polyamide 6,9; polyamide 6,10; polyamide 6,12; polyamide MXD6; PA12,CX;PA12, IT; PPA; PA6, IT; and PA6/PPE.

The functional polymer modifier of the polyamide used in the ball coversor intermediate layers of the present invention can include copolymersor terpolymers having a glycidyl group, hydroxyl group, maleic anhydridegroup or carboxylic group, collectively referred to as functionalizedpolymers. These copolymers and terpolymers may comprise an α-olefin.Examples of suitable α-olefins include ethylene, propylene, 1-butene,1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,3-methyl-1-pentene, 1-octene, 1-decene-, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene,1-hexacocene, 1-octacocene, and 1-triacontene. One or more of theseα-olefins may be used.

Examples of suitable glycidyl groups in copolymers or terpolymers in thepolymeric modifier include esters and ethers of aliphatic glycidyl, suchas allylglycidylether, vinylglycidylether, glycidyl maleate anditaconatem glycidyl acrylate and methacrylate, and also alicyclicglycidyl esters and ethers, such as 2-cyclohexene-1-glycidylether,cyclohexene-4,5 diglyxidylcarboxylate, cyclohexene-4-glycidylcarobxylate, 5-norboenene-2-methyl-2-glycidyl carboxylate, andendocis-bicyclo(2,2,1)-5-heptene-2,3-diglycidyl dicarboxylate. Thesepolymers having a glycidyl group may comprise other monomers, such asesters of unsaturated carboxylic acid, for example, alkyl(meth)acrylatesor vinyl esters of unsaturated carboxylic acids. Polymers having aglycidyl group can be obtained by copolymerization or graftpolymerization with homopolymers or copolymers.

Examples of suitable terpolymers having a glycidyl group include LOTADERAX8900 and AX8920, marketed by Atofina Chemicals, ELVALOY marketed byE.I. Du Pont de Nemours & Co., and REXPEARL marketed by NipponPetrochemicals Co., Ltd. Additional examples of copolymers comprisingepoxy monomers and which are suitable for use within the scope of thepresent invention include styrene-butadiene-styrene block copolymers inwhich the polybutadiene block contains epoxy group, andstyrene-isoprene-styrene block copolymers in which the polyisopreneblock contains epoxy. Commercially available examples of these epoxyfunctional copolymers include ESBS A1005, ESBS A1010, ESBS A1020, ESBSAT018, and ESBS AT019, marketed by Daicel Chemical Industries, Ltd.

Examples of polymers or terpolymers incorporating a maleic anhydridegroup suitable for use within the scope of the present invention includemaleic anhydride-modified ethylene-propylene copolymers, maleicanhydride-modified ethylene-propylene-diene terpolymers, maleicanhydride-modified polyethylenes, maleic anhydride-modifiedpolypropylenes, ethylene-ethylacrylate-maleic anhydride terpolymers, andmaleic anhydride-indene-styrene-cumarone polymers. Examples ofcommercially available copolymers incorporating maleic anhydrideinclude: BONDINE, marketed by Sumitomo Chemical Co., such as BONDINEAX8390, an ethylene-ethyl acrylate-maleic anhydride terpolymer having acombined ethylene acrylate and maleic anhydride content of 32% byweight, and BONDINE TX TX8030, an ethylene-ethyl acrylate-maleicanhydride terpolymer having a combined ethylene acrylate and maleicanhydride content of 15% by weight and a maleic anhydride content of 1%to 4% by weight; maleic anhydride-containing LOTADER 3200, 3210, 6200,8200, 3300, 3400, 3410, 7500, 5500, 4720, and 4700, marketed by AtofinaChemicals; EXXELOR VA 1803, a maleic anyhydride-modifiedethylene-propylene copolymer having a maleic anyhydride content of 0.7%by weight, marketed by Exxon Chemical Co.; and KRATON FG 1901X, a maleicanhydride functionalized triblock copolymer having polystyrene endblocksand poly(ethylene/butylene) midblocks, marketed by Shell Chemical.Preferably the functional polymer component is a maleic anhydridegrafted polymers preferably maleic anhydride grafted polyolefins (forexample, Exxellor VA1803).

Another preferred polymer for blending with the modified block copolymerand/or used as a separate component of the core, outer cover layer orintermediate layer(s) of the golf balls of the present invention is thefamily of polyurethanes or polyureas which typically are prepared byreacting a diisocyanate with a polyol (in the case of polyurethanes) orwith a polyamine (in the case of a polyurea). Thermoplasticpolyurethanes or polyureas may consist solely of this initial mixture ormay be further combined with a chain extender to vary properties such ashardness of the thermoplastic. Thermoset polyurethanes or polyureastypically are formed by the reaction of a diisocyanate and a polyol orpolyamine respectively, and an additional crosslinking agent tocrosslink or cure the material to result in a thermoset.

In what is known as a one-shot process, the three reactants,diisocyanate, polyol or polyamine, and optionally a chain extender or acuring agent, are combined in one step. Alternatively, a two-stepprocess may occur in which the first step involves reacting thediisocyanate and the polyol (in the case of polyurethane) or thepolyamine (in the case of a polyurea) to form a so-called prepolymer, towhich can then be added either the chain extender or the curing agent.This procedure is known as the prepolymer process.

In addition, although depicted as discrete component packages as above,it is also possible to control the degree of crosslinking, and hence thedegree of thermoplastic or thermoset properties in a final composition,by varying the stoichiometry not only of the diisocyanate-to-chainextender or curing agent ratio, but also the initialdiisocyanate-to-polyol or polyamine ratio. Of course in the prepolymerprocess, the initial diisocyanate-to-polyol or polyamine ratio is fixedon selection of the required prepolymer.

In addition to discrete thermoplastic or thermoset materials, it also ispossible to modify a thermoplastic polyurethane or polyurea compositionby introducing materials in the composition that undergo subsequentcuring after molding the thermoplastic to provide properties similar tothose of a thermoset. For example, Kim in U.S. Pat. No. 6,924,337, theentire contents of which are hereby incorporated by reference, disclosesa thermoplastic urethane or urea composition optionally comprising chainextenders and further comprising a peroxide or peroxide mixture, whichcan then undergo post curing to result in a thermoset.

Also, Kim et al. in U.S. Pat. No. 6,939,924, the entire contents ofwhich are hereby incorporated by reference, discloses a thermoplasticurethane or urea composition, optionally also comprising chainextenders, that is prepared from a diisocyanate and a modified orblocked diisocyanate which unblocks and induces further cross linkingpost extrusion. The modified isocyanate preferably is selected from thegroup consisting of: isophorone diisocyanate (IPDI)-based uretdione-typecrosslinker; a combination of a uretdione adduct of IPDI and a partiallye-caprolactam-modified IPDI; a combination of isocyanate adductsmodified by e-caprolactam and a carboxylic acid functional group; acaprolactam-modified Desmodur diisocyanate; a Desmodur diisocyanatehaving a 3,5-dimethylpyrazole modified isocyanate; or mixtures of these.

Finally, Kim et al. in U.S. Pat. No. 7,037,985 B2, the entire contentsof which are hereby incorporated by reference, discloses thermoplasticurethane or urea compositions further comprising a reaction product of anitroso compound and a diisocyanate or a polyisocyanate. The nitrosoreaction product has a characteristic temperature at which it decomposesto regenerate the nitroso compound and diisocyanate or polyisocyanate.Thus, by judicious choice of the post-processing temperature, furthercrosslinking can be induced in the originally thermoplastic compositionto provide thermoset-like properties.

Any isocyanate available to one of ordinary skill in the art is suitablefor use according to the invention. Isocyanates for use with the presentinvention include, but are not limited to, aliphatic, cycloaliphatic,aromatic aliphatic, aromatic, any derivatives thereof, and combinationsof these compounds having two or more isocyanate (NCO) groups permolecule. As used herein, aromatic aliphatic compounds should beunderstood as those containing an aromatic ring, wherein the isocyanategroup is not directly bonded to the ring. One example of an aromaticaliphatic compound is a tetramethylene diisocyanate (TMXDI). Theisocyanates may be organic polyisocyanate-terminated prepolymers, lowfree isocyanate prepolymer, and mixtures thereof. Theisocyanate-containing reactable component also may include anyisocyanate-functional monomer, dimer, trimer, or polymeric adductthereof, prepolymer, quasi-prepolymer, or mixtures thereof.Isocyanate-functional compounds may include monoisocyanates orpolyisocyanates that include any isocyanate functionality of two ormore.

Suitable isocyanate-containing components include diisocyanates havingthe generic structure: O═C═N—R—N═C═O, where R preferably is a cyclic,aromatic, or linear or branched hydrocarbon moiety containing from about1 to about 50 carbon atoms. The isocyanate also may contain one or morecyclic groups or one or more phenyl groups. When multiple cyclic oraromatic groups are present, linear and/or branched hydrocarbonscontaining from about 1 to about 10 carbon atoms can be present asspacers between the cyclic or aromatic groups. In some cases, the cyclicor aromatic group(s) may be substituted at the 2-, 3-, and/or4-positions, or at the ortho-, meta-, and/or para-positions,respectively. Substituted groups may include, but are not limited to,halogens, primary, secondary, or tertiary hydrocarbon groups, or amixture thereof.

Examples of isocyanates that can be used with the present inventioninclude, but are not limited to, substituted and isomeric mixturesincluding 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI);3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate(TDI); polymeric MDI; carbodiimide-modified liquid 4,4′-diphenylmethanediisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylenediisocyanate (MPDI); triphenyl methane-4,4′- and triphenylmethane-4,4″-triisocyanate; naphthylene-1,5-diisocyanate; 2,4′-, 4,4′-,and 2,2-biphenyl diisocyanate; polyphenylene polymethylenepolyisocyanate (PMDI) (also known as polymeric PMDI); mixtures of MDIand PMDI; mixtures of PMDI and TDI; ethylene diisocyanate;propylene-1,2-diisocyanate; trimethylene diisocyanate; butylenesdiisocyanate; bitolylene diisocyanate; tolidine diisocyanate;tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate;tetramethylene-1,4-diisocyanate; pentamethylene diisocyanate;1,6-hexamethylene diisocyanate (HDI); octamethylene diisocyanate;decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate;2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate;dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; diethylidene diisocyanate;methylcyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexanediisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4′-dicyclohexyldiisocyanate; 2,4′-dicyclohexyl diisocyanate; 1,3,5-cyclohexanetriisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl) dicyclohexane;2,4′-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate(IPDI); dimeryl diisocyanate, dodecane-1,12-diisocyanate,1,10-decamethylene diisocyanate, cyclohexylene-1,2-diisocyanate,1,10-decamethylene diisocyanate, 1-chlorobenzene-2,4-diisocyanate,furfurylidene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate,2,2,4-trimethyl hexamethylene diisocyanate, dodecamethylenediisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,3-cyclobutane diisocyanate, 1,4-cyclohexanediisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate),4,4′-methylenebis(phenyl isocyanate), 1-methyl-2,4-cyclohexanediisocyanate, 1-methyl-2,6-cyclohexane diisocyanate,1,3-bis(isocyanato-methyl)cyclohexane,1,6-diisocyanato-2,2,4,4-tetra-methylhexane,1,6-diisocyanato-2,4,4-tetra-trimethylhexane,trans-cyclohexane-1,4-diisocyanate,3-isocyanato-methyl-3,5,5-trimethylcyclo-hexyl isocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexylisocyanate, dicyclohexylmethane 4,4′-diisocyanate,1,4-bis(isocyanatomethyl)cyclohexane, m-phenylene diisocyanate,m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-phenylenediisocyanate, p,p′-biphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenylenediisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate,3,3′-diphenyl-4,4′-biphenylene diisocyanate, 4,4′-biphenylenediisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate,1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate,1,5-tetrahydronaphthalene diisocyanate, metaxylene diisocyanate,2,4-toluene diisocyanate, 2,4′-diphenylmethane diisocyanate,2,4-chlorophenylene diisocyanate, 4,4′-diphenylmethane diisocyanate,p,p′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, 2,2-diphenylpropane-4,4′-diisocyanate,4,4′-toluidine diisocyanate, dianidine diisocyanate, 4,4′-diphenyl etherdiisocyanate, 1,3-xylylene diisocyanate, 1,4-naphthylene diisocyanate,azobenzene-4,4′-diisocyanate, diphenyl sulfone-4,4′-diisocyanate,triphenylmethane 4,4′,4″-triisocyanate, isocyanatoethyl methacrylate,3-isopropenyl-α,α-dimethylbenzyl-isocyanate, dichlorohexamethylenediisocyanate, ω,ω′-diisocyanato-1,4-diethylbenzene, polymethylenepolyphenylene polyisocyanate, isocyanurate modified compounds, andcarbodiimide modified compounds, as well as biuret modified compounds ofthe above polyisocyanates. These isocyanates may be used either alone orin combination. These combination isocyanates include triisocyanates,such as biuret of hexamethylene diisocyanate and triphenylmethanetriisocyanates, and polyisocyanates, such as polymeric diphenylmethanediisocyanate.triisocyanate of HDI; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethanediisocyanate (H₁₂MDI); 2,4-hexahydrotoluene diisocyanate;2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3-, and 1,4-phenylenediisocyanate; aromatic aliphatic isocyanate, such as 1,2-, 1,3-, and1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI);para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurateof any polyisocyanate, such as isocyanurate of toluene diisocyanate,trimer of diphenylmethane diisocyanate, trimer of tetramethylxylenediisocyanate, isocyanurate of hexamethylene diisocyanate, and mixturesthereof, dimerized uretdione of any polyisocyanate, such as uretdione oftoluene diisocyanate, uretdione of hexamethylene diisocyanate, andmixtures thereof; modified polyisocyanate derived from the aboveisocyanates and polyisocyanates; and mixtures thereof.

Any polyol now known or hereafter developed is suitable for useaccording to the invention. Polyols suitable for use in the presentinvention include, but are not limited to, polyester polyols, polyetherpolyols, polycarbonate polyols and polydiene polyols such aspolybutadiene polyols.

Any polyamine available to one of ordinary skill in the polyurethane artis suitable for use according to the invention. Polyamines suitable foruse in the compositions of the present invention include, but are notlimited to, amine-terminated compounds typically are selected fromamine-terminated hydrocarbons, amine-terminated polyethers,amine-terminated polyesters, amine-terminated polycaprolactones,amine-terminated polycarbonates, amine-terminated polyamides, andmixtures thereof. The amine-terminated compound may be a polyether amineselected from polytetramethylene ether diamines, polyoxypropylenediamines, poly(ethylene oxide capped oxypropylene) ether diamines,triethyleneglycoldiamines, propylene oxide-based triamines,trimethylolpropane-based triamines, glycerin-based triamines, andmixtures thereof.

The diisocyanate and polyol or polyamine components may be combined toform a prepolymer prior to reaction with a chain extender or curingagent. Any such prepolymer combination is suitable for use in thepresent invention.

One preferred prepolymer is a toluene diisocyanate prepolymer withpolypropylene glycol. Such polypropylene glycol terminated toluenediisocyanate prepolymers are available from Uniroyal Chemical Company ofMiddlebury, Conn., under the trade name ADIPRENE® LFG963A and LFG640D.Most preferred prepolymers are the polytetramethylene ether glycolterminated toluene diisocyanate prepolymers including those availablefrom Uniroyal Chemical Company of Middlebury, Conn., under the tradename ADIPRENE® LF930A, LF950A, LF601D, and LF751D.

In one embodiment, the number of free NCO groups in the urethane or ureaprepolymer may be less than about 14 percent. Preferably the urethane orurea prepolymer has from about 3 percent to about 11 percent, morepreferably from about 4 to about 9.5 percent, and even more preferablyfrom about 3 percent to about 9 percent, free NCO on an equivalentweight basis.

Polyol chain extenders or curing agents may be primary, secondary, ortertiary polyols. Non-limiting examples of monomers of these polyolsinclude: trimethylolpropane (TMP), ethylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol,dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,1,2-pentanediol, 2,3-pentanediol, 2,5-hexanediol, 2,4-hexanediol,2-ethyl-1,3-hexanediol, cyclohexanediol, and2-ethyl-2-(hydroxymethyl)-1,3-propanediol.

Diamines and other suitable polyamines may be added to the compositionsof the present invention to function as chain extenders or curingagents. These include primary, secondary and tertiary amines having twoor more amines as functional groups. Exemplary diamines includealiphatic diamines, such as tetramethylenediamine,pentamethylenediamine, hexamethylenediamine; alicyclic diamines, such as3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane; or aromatic diamines,such asdiethyl-2,4-toluenediamine-4,4″-methylenebis-(3-chloro,2,6-diethyl)-aniline(available from Air Products and Chemicals Inc., of Allentown, Pa.,under the trade name LONZACURE®), 3,3′-dichlorobenzidene;3,3′-dichloro-4,4′-diaminodiphenyl methane (MOCA);N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine,3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; N,N′-dialkyldiamino diphenylmethane; trimethylene-glycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate, 4,4′-methylenebis-2-chloroaniline, 2,2′,3,3′-tetrachloro-4,4′-diamino-phenyl methane,p,p′-methylenedianiline, p-phenylenediamine or 4,4′-diaminodiphenyl; and2,4,6-tris(dimethylaminomethyl)phenol.

Depending on their chemical structure, curing agents may be slow- orfast-reacting polyamines or polyols. As described in U.S. Pat. Nos.6,793,864, 6,719,646 and copending U.S. Patent Publication No. US2004/0201133 A1, (the contents of all of which are hereby incorporatedherein by reference), slow-reacting polyamines are diamines having aminegroups that are sterically and/or electronically hindered by electronwithdrawing groups or bulky groups situated proximate to the aminereaction sites. The spacing of the amine reaction sites will also affectthe reactivity speed of the polyamines.

Suitable curatives include, but are not limited to,3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; N,N′-dialkyldiamino diphenylmethane; trimethylene-glycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate, and mixtures thereof. Ofthese, 3,5-dimethylthio-2,4-toluenediamine and3,5-dimethylthio-2,6-toluenediamine are isomers and are sold under thetrade name ETHACURE® 300 by Ethyl Corporation. Trimethyleneglycol-di-p-aminobenzoate is sold under the trade name POLACURE 740M andpolytetramethyleneoxide-di-p-aminobenzoates are sold under the tradename POLAMINES by Polaroid Corporation. N,N′-dialkyldiamino diphenylmethane is sold under the trade name UNILINK® by UOP.

Also included as a curing agent for use in the polyurethane or polyureacompositions used in the present invention are the family ofdicyandiamides as described in copending U.S. application Ser. No.11/809,432 filed on May 31, 2007 by Kim et al., the entire contents ofwhich are hereby incorporated by reference.

In one embodiment of the present invention the MBC is used as a singlepolymeric component of a golf ball core, outer cover and one or moreintermediate layers.

In another embodiment of the present invention, the MBC may also beblended with one or more of the heretofore described additional polymercomponents. Thus the core, cover and/or one or more intermediate layercompositions of the golf balls of the present invention may comprisefrom about 30 to about 100, preferably from about 40 to about 90, morepreferably from about 50 to about 85 and most preferably from about 55to about 75 wt % of the MBC and from 0 to about 70, preferably fromabout 10 to about 60, more preferably from about 15 to about 50 and mostpreferably from about 25 to about 45 wt % of one or more additionalpolymer components (all percentages based on the combined weight of theMBC and the ione or more additional polymer components.

The melt index (MFI measured using ASTM D-1238, 230° C. and 2.16 kgload) of the MBC or blend of the MBC with one or more additional polymercomponents is greater than about 5, preferably greater than about 10,most preferably greater than about 15 g/10 min.

In a preferred embodiment the additional polymer component is anolefin/unsaturated acid containing polymer including theethylene/(meth)acrylic acid copolymers and ethylene/(meth)acrylicacid/alkyl(meth)acrylate terpolymers, or ethylene and/or propylenemaleic anhydride copolymers and terpolymers.

In another preferred embodiment the additional polymer component is anolefin/unsaturated acid containing polymer including theethylene/(meth)acrylic acid copolymers and ethylene/(meth)acrylicacid/alkyl(meth)acrylate terpolymers, or ethylene and/or propylenemaleic anhydride copolymers and terpolymers and then from about 0 toabout 100, preferably from about 5 to about 90, more preferably fromabout 10 to about 80 and most preferably from about 12 to about 75weight percent of the acid groups in the resulting blend composition(based on the final weight of the blend composition) are thenneutralized with a basic metal ion salt. The metal cations of the basicmetal ion salt used for neutralization include Li⁺, Na⁺, K⁺, Zn²⁺, Ca²⁺,Co²⁺, Ni²⁺, Cu²⁺, Pb²⁺, and Mg²⁺, with the Li⁺, Na⁺, Ca²⁺, Zn²⁺, andMg²⁺ being preferred. The basic metal ion salts include those of forexample formic acid, acetic acid, nitric acid, and carbonic acid,hydrogen carbonate salts, oxides, hydroxides, and alkoxides.

In another preferred embodiments the additional polymer component is aunimodal ionomer or a bimodal ionomer or a modified unimodal ionomer ora modified bimodal ionomer or any and all combinations thereof.

VIII. Core Composition

The cores of the golf balls of the present invention may include thetraditional rubber components used in golf ball applications including,both natural and synthetic rubbers, such as cis-1,4-polybutadiene,trans-1,4-polybutadiene, 1,2-polybutadiene, cis-polyisoprene,trans-polyisoprene, polychloroprene, polybutylene, styrene-butadienerubber, styrene-butadiene-styrene block copolymer and partially andfully hydrogenated equivalents, styrene-isoprene-styrene block copolymerand partially and fully hydrogenated equivalents, nitrile rubber,silicone rubber, and polyurethane, as well as mixtures of these.Polybutadiene rubbers, especially 1,4-polybutadiene rubbers containingat least 40 mol %, and more preferably 80 to 100 mol % of cis-1,4 bonds,are preferred because of their high rebound resilience, moldability, andhigh strength after vulcanization. The polybutadiene component may besynthesized by using rare earth-based catalysts, nickel-based catalysts,or cobalt-based catalysts, conventionally used in this field.Polybutadiene obtained by using lanthanum rare earth-based catalystsusually employ a combination of a lanthanum rare earth (atomic number of57 to 71)-compound, but particularly preferred is a neodymium compound.

The 1,4-polybutadiene rubbers have a molecular weight distribution(Mw/Mn) of from about 1.2 to about 4.0, preferably from about 1.7 toabout 3.7, even more preferably from about 2.0 to about 3.5, mostpreferably from about 2.2 to about 3.2. The polybutadiene rubbers have aMooney viscosity (ML₁₊₄(100° C.)) of from about 20 to about 80,preferably from about 30 to about 70, even more preferably from about 30to about 60, most preferably from about 35 to about 50. The term “Mooneyviscosity” used herein refers in each case to an industrial index ofviscosity as measured with a Mooney viscometer, which is a type ofrotary plastometer (see JIS K6300). This value is represented by thesymbol ML₁₊₄ (100° C.), wherein “M” stands for Mooney viscosity, “L”stands for large rotor (L-type), “1+4” stands for a pre-heating time of1 minute and a rotor rotation time of 4 minutes, and “100° C.” indicatesthat measurement was carried out at a temperature of 100° C. As readilyappreciated by one skilled in the art, blends of polybutadiene rubbersmay also be utilized in the golf balls of the present invention, suchblends may be prepared with any mixture of rare earth-based catalysts,nickel-based catalysts, or cobalt-based catalysts derived materials, andfrom materials having different molecular weights, molecular weightdistributions and Mooney viscosity.

The cores of the golf balls of the present invention may also include1,2-polybutadienes having differing tacticity, all of which are suitableas unsaturated polymers for use in the presently disclosed compositions,are atactic 1,2-polybutadiene, isotactic 1,2-polybutadiene, andsyndiotactic 1,2-polybutadiene. Syndiotactic 1,2-polybutadiene havingcrystallinity suitable for use as an unsaturated polymer in thepresently disclosed compositions are polymerized from a 1,2-addition ofbutadiene. The presently disclosed golf balls may include syndiotactic1,2-polybutadiene having crystallinity and greater than about 70% of1,2-bonds, more preferably greater than about 80% of 1,2-bonds, and mostpreferably greater than about 90% of 1,2-bonds. Also, the1,2-polybutadiene may have a mean molecular weight between about 10,000and about 350,000, more preferably between about 50,000 and about300,000, more preferably between about 80,000 and about 200,000, andmost preferably between about 10,000 and about 150,000. Examples ofsuitable syndiotactic 1,2-polybutadienes having crystallinity suitablefor use in golf balls are sold under the trade names RB810, RB820, andRB830 by JSR Corporation of Tokyo, Japan.

The cores of the golf balls of the present invention may also includethe polyalkenamer rubbers as previously described herein and disclosedin copending U.S. application Ser. No. 11/335,070, filed on Jan. 18,2006, in the name of Hyun Kim et al., the entire contents of which arehereby incorporated by reference.

When synthetic rubbers such as the aforementioned polybutadienes orpolyalkenamers and their blends are used in the golf balls of thepresent invention they may contain further materials typically oftenused in rubber formulations including crosslinking agents,co-crosslinking agents, peptizers and accelerators.

Suitable cross-linking agents for use in the golf balls of the presentinvention include peroxides, sulfur compounds, or other known chemicalcross-linking agents, as well as mixtures of these. Non-limitingexamples of suitable cross-linking agents include primary, secondary, ortertiary aliphatic or aromatic organic peroxides. Peroxides containingmore than one peroxy group can be used, such as2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-di-(2-tert-butylperoxyisopropyl)benzene. Both symmetrical and asymmetrical peroxides canbe used, for example, tert-butyl perbenzoate and tert-butyl cumylperoxide. Peroxides incorporating carboxyl groups also are suitable. Thedecomposition of peroxides used as cross-linking agents in the presentinvention can be brought about by applying thermal energy, shear,irradiation, reaction with other chemicals, or any combination of these.Both homolytically and heterolytically decomposed peroxide can be usedin the present invention. Non-limiting examples of suitable peroxidesinclude: diacetyl peroxide; di-tert-butyl peroxide; dibenzoyl peroxide;dicumyl peroxide; 2,5-dimethyl-2,5-di(benzoylperoxy)hexane;1,4-bis-(t-butylperoxyisopropyl)benzene; t-butylperoxybenzoate;2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3, such as Trigonox 145-45B,marketed by Akrochem Corp. of Akron, Ohio;1,1-bis(t-butylperoxy)-3,3,5-tri-methylcyclohexane, such as Varox231-XL, marketed by R.T. Vanderbilt Co., Inc. of Norwalk, Conn.; anddi-(2,4-dichlorobenzoyl)peroxide. The cross-linking agents can beblended in total amounts of about 0.05 part to about 5 parts, morepreferably about 0.2 part to about 3 parts, and most preferably about0.2 part to about 2 parts, by weight of the cross-linking agents per 100parts by weight of the unsaturated polymer.

Each cross-linking agent has a characteristic decomposition temperatureat which 50% of the cross-linking agent has decomposed when subjected tothat temperature for a specified time period (t_(1/2)). For example,1,1-bis-(t-butylperoxy)-3,3,5-tri-methylcyclohexane at t_(1/2)=0.1 hrhas a decomposition temperature of 138° C. and2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3 at t_(1/2)=0.1 hr has adecomposition temperature of 182° C. Two or more cross-linking agentshaving different characteristic decomposition temperatures at the samet_(1/2) may be blended in the composition. For example, where at leastone cross-linking agent has a first characteristic decompositiontemperature less than 150° C., and at least one cross-linking agent hasa second characteristic decomposition temperature greater than 150° C.,the composition weight ratio of the at least one cross-linking agenthaving the first characteristic decomposition temperature to the atleast one cross-linking agent having the second characteristicdecomposition temperature can range from 5:95 to 95:5, or morepreferably from 10:90 to 50:50.

Besides the use of chemical cross-linking agents, exposure of thecomposition to radiation also can serve as a cross-linking agent.Radiation can be applied to the unsaturated polymer mixture by any knownmethod, including using microwave or gamma radiation, or an electronbeam device. Additives may also be used to improve radiation curing ofthe diene polymer.

The rubber and cross-linking agent may be blended with aco-cross-linking agent, which may be a metal salt of an unsaturatedcarboxylic acid. Examples of these include zinc and magnesium salts ofunsaturated fatty acids having 3 to 8 carbon atoms, such as acrylicacid, methacrylic acid, maleic acid, and fumaric acid, palmitic acidwith the zinc salts of acrylic and methacrylic acid being mostpreferred. The unsaturated carboxylic acid metal salt can be blended ina rubber either as a preformed metal salt, or by introducing anα,β-unsaturated carboxylic acid and a metal oxide or hydroxide into therubber composition, and allowing them to react in the rubber compositionto form a metal salt. The unsaturated carboxylic acid metal salt can beblended in any desired amount, but preferably in amounts of about 10parts to about 60 parts by weight of the unsaturated carboxylic acid per100 parts by weight of the synthetic rubber.

The core compositions used in the present invention may also incorporateone or more of the so-called “peptizers”. The peptizer preferablycomprises an organic sulfur compound and/or its metal or non-metal salt.Examples of such organic sulfur compounds include thiophenols, such aspentachlorothiophenol, 4-butyl-o-thiocresol, 4t-butyl-p-thiocresol, and2-benzamidothiophenol; thiocarboxylic acids, such as thiobenzoic acid;4,4′ dithio dimorpholine; and, sulfides, such as dixylyl disulfide,dibenzoyl disulfide; dibenzothiazyl disulfide; di(pentachlorophenyl)disulfide; dibenzamido diphenyldisulfide (DBDD), and alkylated phenolsulfides, such as VULTAC marketed by Atofina Chemicals, Inc. ofPhiladelphia, Pa. Preferred organic sulfur compounds includepentachlorothiophenol, and dibenzamido diphenyldisulfide.

Examples of the metal salt of an organic sulfur compound include sodium,potassium, lithium, magnesium calcium, barium, cesium and zinc salts ofthe above-mentioned thiophenols and thiocarboxylic acids, with the zincsalt of pentachlorothiophenol being most preferred.

Examples of the non-metal salt of an organic sulfur compound includeammonium salts of the above-mentioned thiophenols and thiocarboxylicacids wherein the ammonium cation has the general formula [NR¹R²R³R⁴]⁺where R¹, R², R³ and R⁴ are selected from the group consisting ofhydrogen, a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic moiety, and anyand all combinations thereof, with the most preferred being the NH₄⁺-salt of pentachlorothiophenol.

Additional peptizers include aromatic or conjugated peptizers comprisingone or more heteroatoms, such as nitrogen, oxygen and/or sulfur. Moretypically, such peptizers are heteroaryl or heterocyclic compoundshaving at least one heteroatom, and potentially plural heteroatoms,where the plural heteroatoms may be the same or different. Suchpeptizers include peptizers such as an indole peptizer, a quinolinepeptizer, an isoquinoline peptizer, a pyridine peptizer, purinepeptizer, a pyrimidine peptizer, a diazine peptizer, a pyrazinepeptizer, a triazine peptizer, a carbazole peptizer, or combinations ofsuch peptizers.

Suitable peptizers also may include one or more additional functionalgroups, such as halogens, particularly chlorine; a sulfur-containingmoiety exemplified by thiols, where the functional group is sulfhydryl(—SH), thioethers, where the functional group is —SR, disulfides,(R₁S—SR₂), etc.; and combinations of functional groups. Such peptizersare more fully disclosed in copending U.S. Application No. 60/752,475filed on Dec. 20, 2005 in the name of Hyun Kim et al., the entirecontents of which are herein incorporated by reference. A most preferredexample is 2,3,5,6-tetrachloro-4-pyridinethiol (TCPT).

The peptizer, if employed in the golf balls of the present invention ispresent in an amount up to about 10, from about 0.01 to about 10,preferably of from about 0.10 to about 7, more preferably of from about0.15 to about 5 parts by weight per 100 parts by weight of the syntheticrubber component.

The core compositions can also comprise one or more accelerators of oneor more classes. Accelerators are added to an unsaturated polymer toincrease the vulcanization rate and/or decrease the vulcanizationtemperature. Accelerators can be of any class known for rubberprocessing including mercapto-, sulfenamide-, thiuram, dithiocarbamate,dithiocarbamyl-sulfenamide, xanthate, guanidine, amine, thiourea, anddithiophosphate accelerators. Specific commercial accelerators include2-mercaptobenzothiazole and its metal or non-metal salts, such asVulkacit Mercapto C, Mercapto MGC, Mercapto ZM-5, and ZM marketed byBayer AG of Leverkusen, Germany, Nocceler M, Nocceler MZ, and NoccelerM-60 marketed by Ouchisinko Chemical Industrial Company, Ltd. of Tokyo,Japan, and MBT and ZMBT marketed by Akrochem Corporation of Akron, Ohio.A more complete list of commercially available accelerators is given inThe Vanderbilt Rubber Handbook: 13^(th) Edition (1990, R.T. VanderbiltCo.), pp. 296-330, in Encyclopedia of Polymer Science and Technology,Vol. 12 (1970, John Wiley & Sons), pp. 258-259, and in Rubber TechnologyHandbook (1980, Hanser/Gardner Publications), pp. 234-236. Preferredaccelerators include 2-mercaptobenzothiazole (MBT) and its salts. Thesynthetic rubber composition can further incorporate from about 0.1 partto about 10 parts by weight of the accelerator per 100 parts by weightof the rubber. More preferably, the ball composition can furtherincorporate from about 0.2 part to about 5 parts, and most preferablyfrom about 0.5 part to about 1.5 parts, by weight of the accelerator per100 parts by weight of the rubber.

IX. Fillers

The various polymeric compositions used to prepare the golf balls of thepresent invention also can incorporate one or more fillers. Such fillersare typically in a finely divided form, for example, in a size generallyless than about 20 mesh, preferably less than about 100 mesh U.S.standard size, except for fibers and flock, which are generallyelongated. Filler particle size will depend upon desired effect, cost,ease of addition, and dusting considerations. The appropriate amounts offiller required will vary depending on the application but typically canbe readily determined without undue experimentation.

The filler preferably is selected from the group consisting ofprecipitated hydrated silica, limestone, clay, talc, asbestos, barytes,glass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate,zinc sulfide, lithopone, silicates, silicon carbide, diatomaceous earth,carbonates such as calcium or magnesium or barium carbonate, sulfatessuch as calcium or magnesium or barium sulfate, metals, includingtungsten, steel, copper, cobalt or iron, metal alloys, tungsten carbide,metal oxides, metal stearates, and other particulate carbonaceousmaterials, and any and all combinations thereof. Preferred examples offillers include metal oxides, such as zinc oxide and magnesium oxide. Inanother preferred aspect the filler comprises a continuous ornon-continuous fiber. In another preferred aspect the filler comprisesone or more so called nanofillers, as described in U.S. Pat. No.6,794,447 and copending U.S. patent application Ser. No. 10/670,090,filed on Sep. 24, 2003, and copending U.S. patent application Ser. No.10/926,509, filed on Aug. 25, 2004, the entire contents of each of whichare incorporated herein by reference.

Inorganic nanofiller material generally is made of clay, such ashydrotalcite, phyllosilicate, saponite, hectorite, beidellite,stevensite, vermiculite, halloysite, mica, montmorillonite,micafluoride, or octosilicate. To facilitate incorporation of thenanofiller material into a polymer material, either in preparingnanocomposite materials or in preparing polymer-based golf ballcompositions, the clay particles generally are coated or treated by asuitable compatibilizing agent. The compatibilizing agent allows forsuperior linkage between the inorganic and organic material, and it alsocan account for the hydrophilic nature of the inorganic nanofillermaterial and the possibly hydrophobic nature of the polymer.Compatibilizing agents may exhibit a variety of different structuresdepending upon the nature of both the inorganic nanofiller material andthe target matrix polymer. Non-limiting examples include hydroxy-,thiol-, amino-, epoxy-, carboxylic acid-, ester-, amide-, andsiloxy-group containing compounds, oligomers or polymers. The nanofillermaterials can be incorporated into the polymer either by dispersion intothe particular monomer or oligomer prior to polymerization, or by meltcompounding of the particles into the matrix polymer. Examples ofcommercial nanofillers are various Cloisite grades including 10A, 15A,20A, 25A, 30B, and NA+ of Southern Clay Products (Gonzales, Tex.) andthe Nanomer grades including 1.24TL and C.30EVA of Nanocor, Inc.(Arlington Heights, Ill.).

Nanofillers when added into a matrix polymer, such as the polyalkenamerrubber, can be mixed in three ways. In one type of mixing there isdispersion of the aggregate structures within the matrix polymer, but onmixing no interaction of the matrix polymer with the aggregate plateletstructure occurs, and thus the stacked platelet structure is essentiallymaintained. As used herein, this type of mixing is defined as“undispersed”.

However, if the nanofiller material is selected correctly, the matrixpolymer chains can penetrate into the aggregates and separate theplatelets, and thus when viewed by transmission electron microscopy orx-ray diffraction, the aggregates of platelets are expanded. At thispoint the nanofiller is said to be substantially evenly dispersed withinand reacted into the structure of the matrix polymer. This level ofexpansion can occur to differing degrees. If small amounts of the matrixpolymer are layered between the individual platelets then, as usedherein, this type of mixing is known as “intercalation”.

In some circumstances, further penetration of the matrix polymer chainsinto the aggregate structure separates the platelets, and leads to acomplete disruption of the platelet's stacked structure in theaggregate. Thus, when viewed by transmission electron microscopy (TEM),the individual platelets are thoroughly mixed throughout the matrixpolymer. As used herein, this type of mixing is known as “exfoliated”.An exfoliated nanofiller has the platelets fully dispersed throughoutthe polymer matrix; the platelets may be dispersed unevenly butpreferably are dispersed evenly.

While not wishing to be limited to any theory, one possible explanationof the differing degrees of dispersion of such nanofillers within thematrix polymer structure is the effect of the compatibilizer surfacecoating on the interaction between the nanofiller platelet structure andthe matrix polymer. By careful selection of the nanofiller it ispossible to vary the penetration of the matrix polymer into the plateletstructure of the nanofiller on mixing. Thus, the degree of interactionand intrusion of the polymer matrix into the nanofiller controls theseparation and dispersion of the individual platelets of the nanofillerwithin the polymer matrix. This interaction of the polymer matrix andthe platelet structure of the nanofiller is defined herein as thenanofiller “reacting into the structure of the polymer” and thesubsequent dispersion of the platelets within the polymer matrix isdefined herein as the nanofiller “being substantially evenly dispersed”within the structure of the polymer matrix.

If no compatibilizer is present on the surface of a filler such as aclay, or if the coating of the clay is attempted after its addition tothe polymer matrix, then the penetration of the matrix polymer into thenanofiller is much less efficient, very little separation and nodispersion of the individual clay platelets occurs within the matrixpolymer.

Physical properties of the polymer will change with the addition ofnanofiller. The physical properties of the polymer are expected toimprove even more as the nanofiller is dispersed into the polymer matrixto form a nanocomposite.

Materials incorporating nanofiller materials can provide these propertyimprovements at much lower densities than those incorporatingconventional fillers. For example, a nylon-6 nanocomposite materialmanufactured by RTP Corporation of Wichita, Kans., uses a 3% to 5% clayloading and has a tensile strength of 11,800 psi and a specific gravityof 1.14, while a conventional 30% mineral-filled material has a tensilestrength of 8,000 psi and a specific gravity of 1.36. Usingnanocomposite materials with lower inorganic materials loadings thanconventional fillers provides the same properties, and this allowsproducts comprising nanocomposite fillers to be lighter than those withconventional fillers, while maintaining those same properties.

Nanocomposite materials are materials incorporating up to about 20%, orfrom about 0.1% to about 20%, preferably from about 0.1% to about 15%,and most preferably from about 0.1% to about 10% of nanofiller reactedinto and substantially dispersed through intercalation or exfoliationinto the structure of an organic material, such as a polymer, to providestrength, temperature resistance, and other property improvements to theresulting composite. Descriptions of particular nanocomposite materialsand their manufacture can be found in U.S. Pat. Nos. 5,962,553 toEllsworth, 5,385,776 to Maxfield et al., and 4,894,411 to Okada et al.Examples of nanocomposite materials currently marketed include M1030D,manufactured by Unitika Limited, of Osaka, Japan, and 1015C2,manufactured by UBE America of New York, N.Y.

When nanocomposites are blended with other polymer systems, thenanocomposite may be considered a type of nanofiller concentrate.However, a nanofiller concentrate may be more generally a polymer intowhich nanofiller is mixed; a nanofiller concentrate does not requirethat the nanofiller has reacted and/or dispersed evenly into the carrierpolymer.

The nanofiller material is added in an amount up to about 20 wt %, fromabout 0.1% to about 20%, preferably from about 0.1% to about 15%, andmost preferably from about 0.1% to about 10% by weight (based on thefinal weight of the polymer matrix material) of nanofiller reacted intoand substantially dispersed through intercalation or exfoliation intothe structure of the polymer matrix.

If desired, the various polymer compositions used to prepare the golfballs of the present invention can additionally contain otherconventional additives such as plasticizers, pigments, antioxidants,U.V. absorbers, optical brighteners, or any other additives generallyemployed in plastics formulation or the preparation of golf balls.

In an especially preferred aspect, a nanofiller additive component inthe golf ball of the present invention is surface modified with acompatibilizing agent comprising the earlier described block copolymermodifying compounds having the general formula:

(R₂N)_(m)—R′—(X(O)_(n)(OR)_(y))_(m),

A most preferred aspect would be a filler comprising a nanofiller claymaterial surface modified with an amino acid including12-aminododecanoic acid. Such fillers are available from Nanonocor Co.under the tradename Nanomer 1.24TL.

The filler can be blended in variable effective amounts, such as amountsof greater than 0 to at least about 80 parts, and more typically fromabout 10 parts to about 80 parts, by weight per 100 parts by weight ofthe base rubber. If desired, the rubber composition can additionallycontain effective amounts of a plasticizer, an antioxidant, and anyother additives generally used to make golf balls.

The various polymer compositions used to prepare the golf balls of thepresent invention may also be further modified by addition of amonomeric aliphatic and/or aromatic amide as described in copending U.S.application Ser. No. 11/592,109 filed on Nov. 1, 2006 in the name ofHyun Kim et al., the entire contents of which are hereby incorporated byreference.

Golf balls within the scope of the present invention also can include,in suitable amounts, one or more additional ingredients generallyemployed in golf ball compositions. Agents provided to achieve specificfunctions, such as additives and stabilizers, can be present. Examplarysuitable ingredients include colorants, antioxidants, colorants,dispersants, mold releasing agents, processing aids, fillers, and anyand all combinations thereof. Although not required, UV stabilizers, orphoto stabilizers such as substituted hydroxphenyl benzotriazoles may beutilized in the present invention to enhance the UV stability of thefinal compositions. An example of a commercially available UV stabilizeris the stabilizer sold by Ciba Geigy Corporation under the tradenameTINUVIN.

The various formulations for the intermediate layer and/or cover layermay be produced using a twin-screw extruder or may be blended manuallyor mechanically prior to the addition to the injection molder feedhopper. Finished golf balls may be prepared by initially positioning thesolid, preformed core in an injection-molding cavity, followed byuniform injection of the intermediate layer and/or cover layercomposition sequentially over the core. The cover formulations can beinjection molded around the cores to produce golf balls of the requireddiameter.

Alternatively, the cover layers may also be formed around the core byfirst forming half shells by injection molding followed by compressionmolding the half shells about the core to form the final ball.

Covers may also be formed around the cores using compression molding.Cover materials for compression molding may also be extruded or blendedresins or castable resins such as polyurethane.

Typically the golf ball core is made by mixing together the unsaturatedpolymer, cross-linking agents, and other additives with or withoutmelting them. Dry blending equipment, such as a tumbler mixer, Vblender, ribbon blender, or two-roll mill, can be used to mix thecompositions. The golf ball compositions can also be mixed using a mill,internal mixer such as a Banbury or Farrel continuous mixer, extruder orcombinations of these, with or without application of thermal energy toproduce melting. The various core components can be mixed together withthe cross-linking agents, or each additive can be added in anappropriate sequence to the milled unsaturated polymer. In anothermethod of manufacture the cross-linking agents and other components canbe added to the unsaturated polymer as part of a concentrate using dryblending, roll milling, or melt mixing. If radiation is a cross-linkingagent, then the mixture comprising the unsaturated polymer and otheradditives can be irradiated following mixing, during forming into a partsuch as the core of a ball, or after forming.

The resulting mixture can be subjected to, for example, a compression orinjection molding process, to obtain solid spheres for the core. Thepolymer mixture is subjected to a molding cycle in which heat andpressure are applied while the mixture is confined within a mold. Thecavity shape depends on the portion of the golf ball being formed. Thecompression and heat liberates free radicals by decomposing one or moreperoxides, which initiate cross-linking. The temperature and duration ofthe molding cycle are selected based upon the type of peroxide andpeptizer selected. The molding cycle may have a single step of moldingthe mixture at a single temperature for fixed time duration.

For example, a preferred mode of preparation for the cores used in thepresent invention is to first mix the core ingredients on a two-rollmill, to form slugs of approximately 30-40 g, and then compression-moldin a single step at a temperature between 150 to 180° C., for a timeduration between 5 and 12 minutes.

The various core components may also be combined to form a golf ball byan injection molding process, which is also well known to one ofordinary skill in the art. The curing time depends on the variousmaterials selected, and those of ordinary skill in the art will bereadily able to adjust the curing time upward or downward based on theparticular materials used and the discussion herein.

The golf ball of the present invention may comprise from 0 to 5,preferably from 0 to 3, more preferably from 1 to 3, most preferably 1to 2 intermediate layer(s).

In one preferred aspect, at least one of the intermediate layerscomprises the MBC described herein.

In one preferred aspect, the golf ball is a two-piece ball with the MBCused in the cover layer.

In another aspect the golf ball is a three-piece ball with the MBC usedin the outer cover layer and the intermediate or mantle layer comprisesa thermoplastic elastomer including a unimodal ionomer, a bimodalionomer, a modified unimodal ionomer, a modified bimodal ionomer, apolyalkenamer, a polyamide, a thermoplastic or thermoset polyurethane,or any and all combinations thereof.

In another aspect the golf ball is a four-piece ball with the MBC usedin the outer cover layer and at least one of the intermediate or mantlelayers comprises a thermoplastic elastomer including a unimodal ionomer,a bimodal ionomer, a modified unimodal ionomer, a modified bimodalionomer, a polyalkenamer, a polyamide, a thermoplastic or thermosetpolyurethane, or any and all combinations thereof.

In another aspect the golf ball is a five-piece ball with the MBC usedin the outer cover layer and at least one of the intermediate or mantlelayer comprises a thermoplastic elastomer including a unimodal ionomer,a bimodal ionomer, a modified unimodal ionomer, a modified bimodalionomer, a polyalkenamer, a polyamide, a thermoplastic or thermosetpolyurethane, or any and all combinations thereof.

The MBC incorporates between about 85 to about 99, preferably betweenabout 90 and about 98.5, and more preferably between about 92 and about98 wt % of the block copolymer and between about 1 to about 15,preferably between about 1.5 and about 10, and more preferably betweenabout 2 and about 8 wt % of the modifier (all percentages based on thecombined weight of the MBC)

The MBC or blend of the MBC with one or more additional polymercomponents, used in the golf balls of the present invention has amaterial Shore D hardness of from about 25 to about 70, preferably fromabout 30 to about 65, more preferably from about 35 to about 60.

The MBC or blend of the MBC with one or more additional polymercomponents used in the golf balls of the present invention has aflexural modulus from about 500 to about 100,000, preferably from about1,000 to about 80,000, more preferably from about 1,500 to about 60,000psi.

The MBC or blend of the MBC with one or more additional polymercomponents used in the golf balls of the present invention has a tensilestrength of from about 1,000 to about 10,000, preferably from about1,500 to about 7,500, more preferably from about 2,000 to about 6,000psi.

The MBC or blend of the MBC with one or more additional polymercomponents used in the golf balls of the present invention has a tensileelongation of from about 100 to about 1,000, preferably from about 150to about 900, more preferably from about 200 to about 800%.

The melt index of the MBC or blend of the MBC with one or moreadditional polymer components used in the golf balls of the presentinvention is preferably greater 5, more preferably greater than 10, morepreferably greater than 15, and even more preferably greater than 20g/10 min measured at 230° C. under 2.16 kg load.

The core of the balls may have a diameter of from about 0.5 to about1.62, preferably from about 0.7 to about 1.60, more preferably fromabout 1 to about 1.58, yet more preferably from about 1.20 to about1.54, and most preferably from about 1.40 to about 1.50 in.

The core of the balls also may have a PGA compression of less than about140, preferably less than about 120, more preferably less than about100, yet more preferably less than about 90, and most preferably lessthan about 80.

The various core layers (including the center) may each exhibit adifferent hardness. The difference between the center hardness and thatof the next adjacent layer, as well as the difference in hardnessbetween the various core layers may be greater than 2, preferablygreater than 5, most preferably greater than 10 units of Shore D.

In one preferred aspect, the hardness of the center and each sequentiallayer increases progressively outwards from the center to outer corelayer.

In another preferred aspect, the hardness of the center and eachsequential layer decreases progressively inwards from the outer corelayer to the center.

The one or more intermediate layers of the golf balls may have athickness of about 0.01 to about 0.50 or about 0.01 to about 0.20,preferably from about 0.02 to about 0.30 or from about 0.02 to about0.15, more preferably from about 0.03 to about 0.20 or from about 0.03to about 0.10, and most preferably from about 0.03 to about 0.10 orabout 0.03 to about 0.06 in.

The one or more intermediate layers of the golf balls also may have ahardness as measured on the ball of greater than about 25, preferablygreater than about 30, more preferably greater than about 40, and mostpreferably greater than about 50, Shore D units.

The cover layer of the balls may have a thickness of about 0.01 to about0.10, preferably from about 0.02 to about 0.08, more preferably fromabout 0.03 to about 0.06 in.

The cover layer the balls may have a Shore D hardness as measured on theball from about 35 to about 70, preferably from about 45 to about 70 orabout 50 to about 70, more preferably from 47 to about 68 or about 45 toabout 70, and most preferably from about 50 to about 65.

The COR of the golf balls may be greater than about 0.700, preferablygreater than about 0.760, more preferably greater than about 0.780, evenmore preferably greater than 0.790, most preferably greater than 0.795,and especially greater than 0.800 at 125 ft/sec inbound velocity.

The shear cut resistance of the golf balls of the present invention isless than about 4, preferably less than about 3, even more preferablyless than about 2.

EXAMPLES

Examples are given below by way of illustration and not by way oflimitation.

The following materials were used to prepare the Examples andComparative Example:

Septon HG252 is a hydrogenated styrene-isoprene-styrene (SIS) blockcopolymer having a terminal OH group, manufactured by Kuraray Co.

Surlyn® 8150 is a grade of ionomer commercially available from DuPont.

Surlyn® 9150 is a grade of ionomer commercially available from DuPont.

ESCOR 5200 is an ethylene acrylic acid copolymer commercially availablefrom Exxon Mobil Chemical.

NdBR40 is a cis-1,4-polybutadiene rubber made with a rare earth catalystand commercially available from Enichem.

ZnO is a rubber grade zinc oxide purchased from Akrochem (Akron, Ohio).

ZDA are zinc diacrylates was purchased commercially from Sartomer underthe tradenames SR416, and SR638, or Jinyang Chemical, under thetradename ZDA12.

Tetrachlorothiopyridine was purchased commercially from JinyangChemical.

BaSO₄ is Poliwhite 200 barium sulfate purchased from Cinbar.

Varox 231-XL is 1,1-di(t-butylperoxy)-3,3,5-trimethyl-cyclohexanecrosslinking initiator (**40% active peroxide). This is commerciallyavailable from R.T. Vanderbilt and is made by Atofina.

Trigonox 145 is 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexynecrosslinkinginitiator, (**45% active peroxide). This is commerciallyavailable from Akzo Nobel.

Nanomer 1.24TL is a surface treated clay nanofiller, commerciallyavailable from Nanonocor Co.

Color concentrate is TiO₂ with ionomer as binder.

Magnesium Oxide (MgO), and 12-aminododecanoic acid were purchased fromAldrich

The various test properties were measured using the test methods asdefined below.

Core or ball diameter was determined by using standard linear calipersor size gauge.

Compression was measured by applying a spring-loaded force to the golfball center, golf ball core, or the golf ball to be examined, with amanual instrument (an “Atti gauge”) manufactured by the Atti EngineeringCompany of Union City, N.J. This machine, equipped with a Federal DialGauge, Model D81-C, employs a calibrated spring under a known load. Thesphere to be tested is forced a distance of 0.2 inch (5 mm) against thisspring. If the spring, in turn, compresses 0.2 inch, the compression israted at 100; if the spring compresses 0.1 inch, the compression valueis rated as 0. Thus more compressible, softer materials will have lowerAtti gauge values than harder, less compressible materials. Compressionmeasured with this instrument is also referred to as PGA compression.The approximate relationship that exists between Atti or PGA compressionand Riehle compression can be expressed as:

(Atti or PGA compression)=(160-Riehle Compression).

Thus, a Riehle compression of 100 would be the same as an Atticompression of 60.

COR was measured using a golf ball or golf ball subassembly, air cannon,and a stationary steel plate. The steel plate provides an impact surfaceweighing about 100 pounds or about 45 kilograms. A pair of ballisticlight screens, which measure ball velocity, are spaced apart and locatedbetween the air cannon and the steel plate. The ball is fired from theair cannon toward the steel plate over a range of test velocities from50 ft/s to 180 ft/sec (for the tests used herein the velocity was 125ft/sec). As the ball travels toward the steel plate, it activates eachlight screen so that the time at each light screen is measured. Thisprovides an incoming time period proportional to the ball's incomingvelocity. The ball impacts the steel plate and rebounds though the lightscreens, which again measure the time period required to transit betweenthe light screens. This provides an outgoing transit time periodproportional to the ball's outgoing velocity. The coefficient ofrestitution can be calculated by the ratio of the outgoing transit timeperiod to the incoming transit time period, COR=T_(Out)/T_(in).

A “Mooney” viscosity is a unit used to measure the plasticity of raw orunvulcanized rubber. The plasticity in a Mooney unit is equal to thetorque, measured on an arbitrary scale, on a disk in a vessel thatcontains rubber at a temperature of 100° C. and rotates at tworevolutions per minute. The measurement of Mooney viscosity is definedaccording to ASTM D-1646.

Shore D hardness was measured in accordance with ASTM Test D2240.

Melt flow index (I2) was measured in accordance with ASTM D-1238,Condition 230° C.12.16 kg.

Tensile strength, and tensile elongation was measured in accordance withASTM standard D-638, and flexural modulus, using ASTM standard D-790.

Shear cut resistance was determined by examining the balls after theywere impacted by a pitching wedge at controlled speed, classifying eachnumerically from 1 (excellent) to 5 (poor), and averaging the resultsfor a given ball type. Three samples of each Example were used for thistesting. Each ball was hit twice, to collect two impact data points perball. Then, each ball was assigned two numerical scores-one for eachimpact-from 1 (no visible damage) to 5 (substantial material displaced).These scores were then averaged for each Example to produce the shearresistance numbers below. These numbers could then be directly comparedwith the corresponding number for a commercially available ball, theTaylor Made TP Black having a similar construction including the samecore and mantle composition and cover thickness but with a cast urethanecover, which under the same test conditions, had a rating of 1.62.

Examples 1 and 2

Two three-piece golf balls were prepared by initially compressionmolding a 1.42 in diameter core prepared from a mixture of NdBR40 cis1,2-polybutadiene compounded with sufficient peroxide and zincdiacrylate (crosslinker and co-crosslinker respectively),techlorothiopyridine peptizer and BaSO4 and MgO filler to yield a corewith a compression of approximately 50 PGA and a final weight of 29.7 g.

Around this core was then injection molded an intermediate layer ormantle made from a 50/50 wt % blend of two ionomer resins, Surlyn 8150and Surlyn 9150 (commercially available from DuPont). The resultingmantled cores had a diameter of 1.62 inch with the mantle having a ShoreD hardness as measured on the ball of 67D.

An outer cover layer was then injection molded around each mantled core.The outer cover layer was prepared from a blend of 65 wt % of ESCOR5200ethylene/acrylic acid copolymer and 35 wt % of the hydroxylatedstyrene/butadiene block copolymer SEPTON HG252. In Example 1, the blockcopolymer was first modified with 2 wt % of 12-aminododecanoic acid andin the case of Example 2 by 5 wt % of 12-aminododecanoic acid prior toblending with the ethylene/acrylic acid copolymer. To each cover blendwas then added a blend of zinc oxide and sodium carbonate in an amountsufficient to neutralize all of the acid groups in the ESCOR5200 blendcomponent.

Comparative Example 1

In the case of Comparative Example 1, the golf ball was identical tothose of Examples 1 and 2 other than that, rather than the MBC, theunmodified hydroxylated styrene/butadiene block copolymer SEPTON HG252was used to prepare the cover blend.

The various physical properties and test data of the resulting golfballs are summarized in Table 1.

TABLE 1 Three Piece Golf Ball Data with MBC in Cover Ex 1 Ex 2 Comp Ex 1Modified Styrenic Block Copolymer (“MBC”) HG252 SIS block copolymer 9895 (wt %) 12-aminododecanoic acid 2 5 modifier (wt %) Cover CompositionsESCOR5200 (wt %) 35 35 35 MBC (wt %) 65 65 HG252 (SIS block copolymer,65 wt %) Degree of Neutralization 100% 100% 100% Mechanical propertiesMFI (g/10 min) 11.2 11.1 8 TS (psi) 2582 2697 2284 TE (%) 517 516 421 EM(kpsi) 0.3 0.3 0.32 FS (psi) 151 159 149 FM (kpsi) 18.2 18.8 17.1 ShoreD 40.5 44.1 40 Mantle Compositions Surlyn 8150 50 50 50 Surlyn 9150 5050 50 Mantle Physicals Pole Size (in) 1.6 1.6 1.6 Compression (PGA) 8686 86 COR (125 ft/s) 0.815 0.815 0.815 Shore D (on the ball) 71 71 71Ball Physicals Compression (PGA) 81 80 81 COR (125 ft/s) 0.804 0.8050.805 Shore D 54.2 52.9 51.2 Ball Performance Shear Value* 2.2 1.9 2.4160 mph Driver Spin Spin rate (rpm) 3086 3037 3157 Speed (miles/hr)160.1 160.4 159.6 175 mph Driver Spin Spin rate (rpm) 3361 3253 3338Speed (miles/hr) 174.9 175.2 174.7 *The NXT Tour ball commerciallyavailable from Titleist had a Shear Value of 4.8. The TP Black casturethane covered golf ball available from Taylor Made Golf Co. Inc. hada Shear Value of 2.6.

Comparison of the data in Table 1 show that the modified block copolymerblends show improved processability over the unmodified analog as shownby the high melt index values while maintaining excellent tensilestrength flex modulus and hardness properties. The resulting golf ballshad excellent spin and ball velocities comparable to the unmodifiedanalogs while exhibiting improved shear cut resistance comparable inperformance to those of a premium golf ball having a cast urethanecover.

One aspect of the invention concerns a two-piece golf ball comprising acore and one cover layer, wherein the core has a PGA compression of lessthan 90, and the core/cover layer combined construct has a PGAcompression of at least 30.

Another aspect of the invention concerns a three-piece golf ballcomprising a core, an intermediate mantle layer, and a cover layer;wherein the core has a PGA compression of less than 80, and thecore/intermediate mantle layer combined construct has a PGA compressionof at least 30.

Another aspect of the invention concerns a golf ball comprising a coreor core layers having diameter of from about 0.5 to about 1.62,preferably from about 0.7 to about 1.60, more preferably from about 1 toabout 1.58, yet more preferably from about 1.20 to about 1.54, and mostpreferably from about 1.40 to about 1.50 in.

Another aspect of the invention concerns a golf ball having a PGAcompression of less than about 140, preferably less than about 120, morepreferably less than about 100, yet more preferably less than about 90,and most preferably less than about 80.

Another aspect of the invention concerns a golf ball comprising corelayer(s) surrounding and having a hardness difference between the centerhardness and that of the next adjacent layer greater than 2, preferablygreater than 5, most preferably greater than 10 units of Shore D.

Another aspect of the invention concerns a golf ball comprising corelayer(s) having a hardness difference between the core layers greaterthan 2, preferably greater than 5, most preferably greater than 10 unitsof Shore D.

Another aspect of the invention concerns a golf ball having the hardnessof the center and each sequential layer increasing progressively outwardfrom the center to outer core layer.

Another aspect of the invention concerns a golf ball having the hardnessof the center and each sequential layer decreasing progressively inwardfrom the outer core layer to the center.

Another aspect of the invention concerns a golf ball comprising a one ormore intermediate layers having thickness of about 0.01 to about 0.50 orabout 0.01 to about 0.20, preferably from about 0.02 to about 0.30 orfrom about 0.02 to about 0.15, more preferably from about 0.03 to about0.20 or from about 0.03 to about 0.10, and most preferably from about0.03 to about 0.10 or about 0.03 to about 0.06 in.

Another aspect of the invention concerns a golf ball comprising one ormore intermediate layers having a hardness as measured on the ball ofgreater than about 25, preferably greater than about 30, more preferablygreater than about 40, and most preferably greater than about 50, ShoreD units.

Another aspect of the invention concerns a golf ball comprising a coverlayer having a thickness of about 0.01 to about 0.10, preferably fromabout 0.02 to about 0.08, more preferably from about 0.03 to about 0.06in.

Another aspect of the invention concerns a golf ball comprising a coverlayer having a Shore D hardness as measured on the ball from about 35 toabout 70, preferably from about 45 to about 70 or about 50 to about 70,more preferably from 47 to about 68 or about 45 to about 70, and mostpreferably from about 50 to about 65.

Another aspect of the invention concerns a golf ball comprising CORgreater than about 0.700, preferably greater than about 0.760, morepreferably greater than about 0.780, even more preferably greater than0.790, even more preferably greater than 0.795, and more preferablygreater than 0.800 at 125 ft/sec inbound velocity.

Another aspect of the invention concerns a golf ball comprising a coreor core layers, one or more intermediate mantle layer, one or more outermantle layer; and a cover layer;

wherein the core has a PGA compression of less than 70, and thecore/intermediate mantle layer/outer mantle layer combined construct hasa PGA compression of at least 30.

Another aspect of the invention concerns a golf ball comprising a coreor core layers having diameter of from about 0.5 to about 1.62,preferably from about 0.7 to about 1.60, more preferably from about 1 toabout 1.58, yet more preferably from about 1.20 to about 1.54, and mostpreferably from about 1.40 to about 1.50 in.

Another aspect of the invention concerns a golf ball comprising a PGAcompression of less than about 140, preferably less than about 120, morepreferably less than about 100, yet more preferably less than about 90,and most preferably less than about 80.

Another aspect of the invention concerns a golf ball comprising corelayer(s) surrounding having a hardness difference between the centerhardness and that of the next adjacent layer greater than 2, preferablygreater than 5, most preferably greater than 10 units of Shore D.

Another aspect of the invention concerns a golf ball comprising corelayer(s) having a hardness difference between the core layers greaterthan 2, preferably greater than 5, most preferably greater than 10 unitsof Shore D.

Another aspect of the invention concerns a golf ball comprising thehardness of the center and each sequential layer increasingprogressively outward from the center to outer core layer.

Another aspect of the invention concerns a golf ball comprising thehardness of the center and each sequential layer decreasingprogressively inwards from the outer core layer to the center.

Another aspect of the invention concerns a golf ball comprising one ormore intermediate layers having thickness of about 0.01 to about 0.50 orabout 0.01 to about 0.20, preferably from about 0.02 to about 0.30 orfrom about 0.02 to about 0.15, more preferably from about 0.03 to about0.20 or from about 0.03 to about 0.10, and most preferably from about0.03 to about 0.10 or about 0.03 to about 0.06 in.

Another aspect of the invention concerns a golf ball comprising one ormore intermediate layers having a hardness as measured on the ball ofgreater than about 25, preferably greater than about 30, more preferablygreater than about 40, and most preferably greater than about 50, ShoreD units.

Another aspect of the invention concerns a golf ball comprising a coverlayer having a thickness of about 0.01 to about 0.10, preferably fromabout 0.02 to about 0.08, more preferably from about 0.03 to about 0.06in.

Another aspect of the invention concerns a golf ball comprising a coverlayer having a Shore D hardness as measured on the ball from about 35 toabout 70, preferably from about 45 to about 70 or about 50 to about 70,more preferably from 47 to about 68 or about 45 to about 70, and mostpreferably from about 50 to about 65.

Another aspect of the invention concerns a golf ball comprising CORgreater than about 0.700, preferably greater than about 0.760, morepreferably greater than about 0.780, even more preferably greater than0.790, even more preferably greater than 0.795, and more preferablygreater than 0.800 at 125 ft/sec inbound velocity.

Another aspect of the invention concerns a golf ball comprising (a) acore; (b) an inner mantle layer; (c) at least one intermediate mantlelayer; (d) an outer mantle layer; and (e) at least one cover layer;wherein the core has a PGA compression of less than 70, and thecore/inner mantle layer/intermediate mantle layer combined construct hasa PGA compression of at least 30.

Another aspect of the invention concerns a golf ball wherein the corehas a PGA compression of less than 60.

Another aspect of the invention concerns a golf ball wherein the corehas a PGA compression of less than 40.

Another aspect of the invention concerns a golf ball wherein each of themantle layers each has a thickness of less than 0.080 in.

Another aspect of the invention concerns a golf ball wherein thecore/inner mantle layer/intermediate mantle layer combined construct hasa PGA compression of at least 40.

Another aspect of the invention concerns a golf ball wherein thecore/inner mantle layer/intermediate mantle layer combined construct hasa PGA compression of at least 50.

Another aspect of the invention concerns a golf ball wherein thecore/inner mantle layer/intermediate mantle layer combined construct hasa PGA compression of 30 to 70.

Another aspect of the invention concerns a golf ball wherein the innermantle layer, the intermediate mantle layer, the outer mantle layer, andthe outer cover layer each individually comprises thermosetpolyurethanes and thermoset polyureas, unimodal ethylene/carboxylic acidcopolymers, unimodal ethylene/carboxylic acid/carboxylate terpolymers,bimodal ethylene/carboxylic acid copolymers, bimodal ethylene/carboxylicacid/carboxylate terpolymers, unimodal ionomers, bimodal ionomers,modified unimodal ionomers, modified bimodal ionomers, polyurethaneionomer, thermoplastic polyurethanes, thermoplastic polyureas,polyamides, copolyamides, polyesters, copolyesters, polycarbonates,polyolefins, halogenated polyolefins, halogenated polyethylenes,polyphenylene oxide, polyphenylene sulfide, diallyl phthalate polymer,polyimides, polyvinyl chloride, polyamide-ionomer, polyvinyl alcohol,polyarylate, polyacrylate, polyphenylene ether, impact-modifiedpolyphenylene ether, polystyrene, high impact polystyrene,acrylonitrile-butadiene-styrene copolymer styrene-acrylonitrile (SAN),acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S/MA)polymer, styrenic copolymer, functionalized styrenic copolymer,functionalized styrenic terpolymer, styrenic terpolymer, cellulosepolymer, liquid crystal polymer (LCP), ethylene-propylene-dieneterpolymer (EPDM), ethylene-vinyl acetate copolymers (EVA),ethylene-propylene copolymer, ethylene vinyl acetate, polyurea,polysiloxane, a copolymer comprising at least one first co-monomerselected from butadiene, isoprene, ethylene or butylene and at least onesecond co-monomer selected from a (meth)acrylate or a vinyl arylene; orany and all combinations or mixtures thereof, a polyalkenamer rubberselected from the group consisting of polybutenamer rubber,polypentenamer rubber, polyhexenamer rubber, polyheptenamer rubber,polyoctenamer rubber, polynonenamer rubber, polydecenamer rubberpolyundecenamer rubber, polydodecenamer rubber, polytridecenamer rubberand any and all combinations of such materials.

Another aspect of the invention concerns a golf ball wherein the outermantle layer has a material Shore D hardness of at least 55 and amaterial flexural modulus of at least 35 kpsi.

Another aspect of the invention concerns a golf ball wherein each of(a), (b), (c) and (d) has a Shore D hardness and the Shore D hardness ofeach of (a), (b), (c) and (d) increases from the core to the outermantle layer.

Another aspect of the invention concerns a golf ball wherein each of(a), (b), (c) and (d) have a Shore D hardness and the Shore D hardnessof each of (a), (b), (c) and (d) follows the relationships of(a)<(c)<(b)<(d), (a)<(b)<(d)<(c), (a)<(d)<(c)<(b), and (a)<(d)<(b)<(c).

Another aspect of the invention concerns a golf ball comprising (a) acore material having a PGA compression of less than 70 and a materialflexural modulus of less than 20 kpsi; (b) an inner mantle layermaterial; (c) at least one intermediate mantle layer material; (d) anouter mantle layer material; and (e) at least one cover layer material;wherein the material of each of (a), (b), (c) and (d) have a materialflexural modulus and the material flexural modulus of each of (a), (b),(c) and (d) increases from the core material to the outer mantle layermaterial such that each successive layer between the core material andthe outer mantle layer material has a flexural modulus that is greaterrelative to the immediately adjacent inner layer material.

Another aspect of the invention concerns a golf ball wherein each of(a), (b), (c) and (d) have a flexural modulus and the flexural modulusof each of (a), (b), (c) and (d) follows the relationships of(a)<(c)<(b)<(d), (a)<(b)<(d)<(c), (a)<(d)<(c)<(b), and (a)<(d)<(b)<(c).

Another aspect of the invention concerns a golf ball wherein the corehas a PGA compression of less than 40.

Another aspect of the invention concerns a golf ball wherein each of themantle layers each has a thickness of less than 0.075 in.

Another aspect of the invention concerns a golf ball wherein the innermantle layer has a material flexural modulus of 2 to 35 kpsi.

Another aspect of the invention concerns a golf ball wherein theintermediate mantle layer has a material flexural modulus of 10 to 50kpsi.

Another aspect of the invention concerns a golf ball wherein the outermantle layer has a material flexural modulus of 30 to 110 kpsi.

Another aspect of the invention concerns a golf ball wherein the corematerial has a flexural modulus of less than 10 kpsi and a PGAcompression of less than 40.

Another aspect of the invention concerns a golf ball wherein the innermantle layer, the intermediate mantle layer, the outer mantle layer, andthe outer cover layer each individually comprises a thermosetpolyurethanes and thermoset polyureas, unimodal ethylene/carboxylic acidcopolymers, unimodal ethylene/carboxylic acid/carboxylate terpolymers,bimodal ethylene/carboxylic acid copolymers, bimodal ethylene/carboxylicacid/carboxylate terpolymers, unimodal ionomers, bimodal ionomers,modified unimodal ionomers, modified bimodal ionomers, polyurethaneionomer, thermoplastic polyurethanes, thermoplastic polyureas,polyamides, copolyamides, polyesters, copolyesters, polycarbonates,polyolefins, halogenated polyolefins, halogenated polyethylenes,polyphenylene oxide, polyphenylene sulfide, diallyl phthalate polymer,polyimides, polyvinyl chloride, polyamide-ionomer, polyvinyl alcohol,polyarylate, polyacrylate, polyphenylene ether, impact-modifiedpolyphenylene ether, polystyrene, high impact polystyrene,acrylonitrile-butadiene-styrene copolymer styrene-acrylonitrile (SAN),acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S/MA)polymer, styrenic copolymer, functionalized styrenic copolymer,functionalized styrenic terpolymer, styrenic terpolymer, cellulosepolymer, liquid crystal polymer (LCP), ethylene-propylene-dieneterpolymer (EPDM), ethylene-vinyl acetate copolymers (EVA),ethylene-propylene copolymer, ethylene vinyl acetate, polyurea,polysiloxane, a copolymer comprising at least one first co-monomerselected from butadiene, isoprene, ethylene or butylene and at least onesecond co-monomer selected from a (meth)acrylate or a vinyl arylene; orany and all combinations or mixtures thereof, a polyalkenamer rubberselected from the group consisting of polybutenamer rubber,polypentenamer rubber, polyhexenamer rubber, polyheptenamer rubber,polyoctenamer rubber, polynonenamer rubber, polydecenamer rubberpolyundecenamer rubber, polydodecenamer rubber, polytridecenamer rubberand any and all combinations of such materials.

Another aspect of the invention concerns a golf ball wherein the outermantle layer has a material Shore D hardness of at least 55 and aflexural modulus of at least 55 kpsi.

Another aspect of the invention concerns a golf ball wherein eachsuccessive layer between the core material and the outer mantle layermaterial has a flexural modulus that is greater by at least 3 kpsirelative to the immediately adjacent inner layer material.

Another aspect of the invention concerns a five-piece golf ballcomprising: (a) a core material having a flexural modulus of less than15 kpsi; (b) an inner mantle layer material adjacent to the corematerial, wherein the inner mantle layer material has a flexural modulusof 2-35 kpsi; (c) an intermediate mantle layer material adjacent to theinner mantle layer material, wherein the intermediate mantle layermaterial has a flexural modulus of 10-50 kpsi; (d) an outer mantle layermaterial adjacent to the intermediate mantle layer material, wherein theouter mantle layer material has a flexural modulus of 20-110 kpsi; and(e) an outer cover layer material.

Another aspect of the invention concerns a golf ball wherein the corematerial has a flexural modulus of less than 8 kpsi, the inner mantlelayer material has a flexural modulus of 5-25 kpsi, the intermediatemantle layer material has a flexural modulus of 15-45 kpsi, and theouter mantle layer has a flexural modulus of 35-80 kpsi.

Another aspect of the invention concerns a golf ball wherein there is anincreasing material Shore D hardness from the core material to the outermantle layer material, and an increasing flexural modulus from the corematerial to the outer mantle layer material.

Another aspect of the invention concerns a golf ball wherein the Shore Dhardness and the flexural modulus of each of (a), (b), (c) and (d)follows the relationships of (a)<(c)<(b)<(d), (a)<(b)<(d)<(c),(a)<(d)<(c)<(b), and (a)<(d)<(b)<(c) 10.

Another aspect of the invention concerns a golf ball wherein the corematerial has a PGA compression of less than 50.

Another aspect of the invention concerns a golf ball wherein each of themantle layers each has a thickness of less than 0.080 in.

Another aspect of the invention concerns a golf ball wherein the innermantle layer, the intermediate mantle layer, the outer mantle layer, andthe outer cover layer each individually comprises a thermosetpolyurethanes and thermoset polyureas, unimodal ethylene/carboxylic acidcopolymers, unimodal ethylene/carboxylic acid/carboxylate terpolymers,bimodal ethylene/carboxylic acid copolymers, bimodal ethylene/carboxylicacid/carboxylate terpolymers, unimodal ionomers, bimodal ionomers,modified unimodal ionomers, modified bimodal ionomers, polyurethaneionomer, thermoplastic polyurethanes, thermoplastic polyureas,polyamides, copolyamides, polyesters, copolyesters, polycarbonates,polyolefins, halogenated polyolefins, halogenated polyethylenes,polyphenylene oxide, polyphenylene sulfide, diallyl phthalate polymer,polyimides, polyvinyl chloride, polyamide-ionomer, polyvinyl alcohol,polyarylate, polyacrylate, polyphenylene ether, impact-modifiedpolyphenylene ether, polystyrene, high impact polystyrene,acrylonitrile-butadiene-styrene copolymer styrene-acrylonitrile (SAN),acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S/MA)polymer, styrenic copolymer, functionalized styrenic copolymer,functionalized styrenic terpolymer, styrenic terpolymer, cellulosepolymer, liquid crystal polymer (LCP), ethylene-propylene-dieneterpolymer (EPDM), ethylene-vinyl acetate copolymers (EVA),ethylene-propylene copolymer, ethylene vinyl acetate, polyurea,polysiloxane, a copolymer comprising at least one first co-monomerselected from butadiene, isoprene, ethylene or butylene and at least onesecond co-monomer selected from a (meth)acrylate or a vinyl arylene; orany and all combinations or mixtures thereof, a polyalkenamer rubberselected from the group consisting of polybutenamer rubber,polypentenamer rubber, polyhexenamer rubber, polyheptenamer rubber,polyoctenamer rubber, polynonenamer rubber, polydecenamer rubberpolyundecenamer rubber, polydodecenamer rubber, polytridecenamer rubberand any and all combinations of such materials.

Another of the invention aspect concerns a golf ball wherein the outermantle layer has a material Shore D hardness of at least 55 and aflexural modulus of at least 35 kpsi.

Another aspect of the invention concerns a golf ball wherein the outermantle layer material has a flexural modulus of 30-80 kpsi.

Another aspect of the invention concerns a golf ball comprising (a) acore having a PGA compression of less than 40; (b) an inner mantlelayer; (c) an intermediate mantle layer; (d) an outer mantle layer; and(e) an outer cover layer; and wherein the golf ball has sufficientimpact durability and a golf ball frequency of <4000 Hz.

Another aspect of the invention concerns a golf ball wherein the golfball frequency is less than 3400 Hz.

Another aspect of the invention concerns a golf ball wherein the golfball has a sound pressure level, S, of less than 81 dB.

Another aspect of the invention concerns a golf ball wherein the corecomprises polybutadiene; the inner mantle layer and the intermediatemantle layer each individually comprise a unimodal ionomer; a bimodalionomer; a modified unimodal ionomer; a modified bimodal ionomer; athermoset polyurethane; a polyester elastomer; a copolymer comprising atleast one first co-monomer selected from butadiene, isoprene, ethylene,propylene or butylene and at least one second co-monomer selected from a(meth)acrylate or a vinyl arylene; a polyalkenamer; or any and allcombinations or mixtures thereof; the outer mantle layer comprises acopolymer of ethylene and (meth)acrylic acid partially neutralized witha metal selected from the group consisting of lithium, sodium,potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum or acombination thereof; or a blend of a polyamide and at least one maleicanhydride grafted polyolefin; and the outer cover layer comprises athermoset polyurethane; a thermoset polyurea; a polymer blendcomposition formed from a copolymer of ethylene and carboxylic acid asComponent A, a hydroxyl-modified block copolymer of styrene and isopreneas Component B, and a metal cation as Component C; or a polymer blendcomposition formed from a copolymer of ethylene and carboxylic acid asComponent A, a styrene-(ethylene-butylene)-styrene block copolymer asComponent B, and a metal cation as Component C.

Another aspect of the invention concerns a golf ball wherein thepolybutadiene of the core is obtained via a lanthanum rare earthcatalyst.

Another aspect of the invention concerns a golf ball wherein thepolybutadiene of the core further comprises a pyridine peptizer thatalso includes a chlorine functional group and a thiol functional group.

Another aspect of the invention concerns a golf ball wherein the innermantle layer and the intermediate mantle layer each individuallycomprise polyoctenamer; a hydroxyl-modified block copolymer of styreneand isoprene; a high acid content modified ionomers; or a mixturethereof.

Another aspect of the invention concerns a golf ball wherein the corecomprises polybutadiene; the inner mantle layer and the intermediatemantle layer each individually comprise a unimodal ionomer; a bimodalionomer; a modified unimodal ionomer; a modified bimodal ionomer; athermoset polyurethane; a polyester elastomer; a copolymer comprising atleast one first co-monomer selected from butadiene, isoprene, ethylene,propylene or butylene and at least one second co-monomer selected from a(meth)acrylate or a vinyl arylene; a polyalkenamer; or any and allcombinations or mixtures thereof; the outer mantle layer comprises acopolymer of ethylene and (meth)acrylic acid partially neutralized witha metal selected from the group consisting of lithium, sodium,potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum or acombination thereof; or a blend of a polyamide and at least one maleicanhydride grafted polyolefin; and the outer cover layer comprises athermoset polyurethane; a thermoset polyurea; a polymer blendcomposition formed from a copolymer of ethylene and carboxylic acid asComponent A, a hydroxyl-modified block copolymer of styrene and isopreneas Component B, and a metal cation as Component C; or a polymer blendcomposition formed from a copolymer of ethylene and carboxylic acid asComponent A, a styrene-(ethylene-butylene)-styrene block copolymer asComponent B, and a metal cation as Component C.

1. A golf ball, comprising: a core comprising a center; an outer coverlayer; optionally one or more intermediate layers; and wherein one ormore of the core, outer cover layer or one or more intermediate layerscomprises a blend composition comprising (A) from about 85 to about 99wt % (based on the combined weight of Components A and B) of a blockcopolymer; and (B) from about 1 to about 15 wt % (based on the combinedweight of Components A and B) of one or more modifying agents selectedfrom the group consisting of amino acids, aminotriazines, dicyandiamidesand polyamines and any and all combinations thereof.
 2. The golf ballaccording to claim 1 wherein one or more of the core, outer cover layeror one or more intermediate layers comprises a blend compositioncomprising: (A) from about 90 to about 98.5 wt % (based on the combinedweight of Components A and B) of a block copolymer comprising (a) afirst polymer block having an aromatic vinyl compound, and (b) a secondpolymer block having an olefinic or a conjugated diene compound, or anycombination thereof; and (B) from about 1.5 to about 10 wt % (based onthe combined weight of Components A and B) of one or more modifyingagents selected from the group consisting of 1) a compound having thegeneral formula(R₂N)_(m)—R′—(X(O)_(n)(OR)_(y))_(m),  where R is hydrogen, or a C₁-C₂₀aliphatic, cycloaliphatic or aromatic group; R′ is a bridging groupcomprising one or more C₁-C₂₀ straight chain or branched aliphatic oralicyclic groups, or C₁-C₂₀ substituted straight chain or branchedaliphatic or alicyclic groups, or C₁-C₂₀ aromatic groups, or an oligomerof up to 12 repeating units, and X is C or S or P with the proviso thatwhen X=C, n=1 and y=1 and when X=S, n=2 and y=1, and when X=P, n=0-1 andy=2 or 4, and m=1-3, 2) an aminotriazene having the general formula

where R₁-R₅ are independently aliphatic, substituted aliphatic, alkoxy,amine, aryl, substituted aryl, heteroaryl, substituted heteroarylgroups, hydrogen or halogen; 3) a dicyandiamide having the generalformula

where R and R′ independently are hydrogen, or a C₁-C₂₀ aliphatic,cycloaliphatic or aromatic moiety or substituted aliphatic,cycloaliphatic or aromatic moiety, R is H, —CH₃, —C₂H₅, —C₆H₅, —CH₂X,—C₂H₄X, —C₆H₄X, —CH₂C₆H₄X, —CH₂CH₂C₆H₄X, or any and all combinationsthereof, and where X is hydrogen, a methyl group, an ethyl group, amethoxy group, an ethoxy group, an amino group and a dimethylaminogroup; 4) a polyamine; and 5) any and all combinations thereof.
 3. Thegolf ball according to claim 1 wherein one the core, outer cover layeror one or more intermediate layers comprises a blend compositioncomprising: (A) from about 92 to about 98 wt % (based on the combinedweight of Components A and B) of a block copolymer comprising (a) afirst polymer block selected from the group consisting of styrene,α-methylstyrene, o-, m- or p-methylstyrene, 4-propylstyrene,1,3-dimethylstyrene vinylnaphthalene and vinylanthracene; and (b) asecond polymer block having an olefinic group selected from the groupconsisting of ethylene, propylene, and butene or a conjugated dienecompound, selected from the group consisting of 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene and anycombination thereof; and (B) from about 2 to about 8 wt % (based on thecombined weight of Components A and B) of one or more modifying agentsselected from the group consisting of 1)4,4′-methylene-bis-(cyclohexylamine)carbamate, 11-aminoundecanoic acid,12-aminododecanoic acid, epsilon-caprolactam; omega-caprolactam, and anyand all combinations thereof; 2) guanamine,6-methyl-1,3,5-triazine-2,4-diamine (acetoguanamine),6-nonyl-1,3,5-triazine-2,4-diamine (nonylguanamine),6-phenyl-1,3,5-triazine-2,4-diamine (benzoguanamine), or2,4,6-triamino-triazine (melamine) and any and all combinations thereof;3) dicyandiamide, N-benzyldicyandiamide,N-(4-methylbenzyl)dicyandiamide, N-(4-methoxybenzyl)dicyandiamide,N-phenethyldicyandiamide; N-(4-methylphenethyl)dicyandiamide; andN-(4-methoxyphenethyl)dicyandiamide and any and all combinationsthereof; 4) any and all combinations thereof.
 4. The golf ball accordingto claim 3 wherein the outer cover layer has a Shore D hardness asmeasured on the ball of from about 35 to about 70 and comprises a blendcomposition comprising: (A) a block copolymer selected from the groupconsisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene(SIS), styrene-ethylene-butylene-styrene, (SEBS) andstyrene-ethylene/propylene-styrene (SEPS), a hydrogenated hydroxylfunctionalized styrene-isoprene-styrene; and any combination thereof;and (B) one or more modifying agents selected from the group consistingof, 11-aminoundecanoic acid, 12-aminododecanoic guanamine,dicyandiamide, and any and all combinations thereof, and furthercomprises (C) one or more additional polymers selected from the groupconsisting of olefin/unsaturated acid containing polymer including theethylene/(meth)acrylic acid copolymers and ethylene/(meth)acrylicacid/alkyl(meth)acrylate terpolymers, or ethylene and/or propylenemaleic anhydride copolymers and terpolymers, a unimodal ionomer or abimodal ionomer or a modified unimodal ionomer or a modified bimodalionomer or any and all combinations thereof; and wherein the blendcomposition has a melt index of greater than about 3 g/10 min, aflexural modulus of from about 500 to about 100,000 psi, a materialShore D hardness of from about 25 to about
 70. 5. The golf ballaccording to claim 1, wherein core, one of the intermediate layers, andouter cover layer comprise a polyalkenamer rubber selected from thegroup consisting of polybutenamer rubber, polypentenamer rubber,polyhexenamer rubber, polyheptenamer rubber, polyoctenamer rubber,polynonenamer rubber, polydecenamer rubber polyundecenamer rubber,polydodecenamer rubber, polytridecenamer rubber and any and allcombinations thereof.
 6. A golf ball, comprising: a core comprising acenter; an outer cover layer; optionally one or more intermediatelayers; and wherein one or more of the core, outer cover layer or one ormore intermediate layers comprises a modified resin made by a methodcomprising reacting an amine-functionalized modifier with a blockcopolymer having at least one block A comprising an aromatic vinylcompound and at least one polymer block B comprising a hydrogenateddiene compound, with or without having a hydroxyl group at the terminalof the block copolymer.
 7. The golf ball according to claim 6 furthercomprising blending the modified resin with a non-neutralizedcopolymeric or terpolymeric olefin-containing acid.
 8. The golf ballaccording to claim 7 further comprising at least partially neutralizingthe acid.
 9. The golf ball according to claim 6 further comprising fullyneutralizing the acid.
 10. The golf ball according to claim 6 furthercomprising blending the modified resin with a partially or fullyneutralized copolymeric or terpolymeric olefin-containing acid.
 11. Thegolf ball according to claim 6 wherein the block copolymer is a styrenicblock copolymer.
 12. The golf ball according to claim 6 wherein theamine-functionalized modifier is selected from amino acids,aminotriazines, dicyandiamides, polyamines, and any and all combinationsthereof.
 13. The golf ball according to claim 6 where the modified resinis made by a method comprising reacting: (A) from about 85 to about 99wt % (based on combined weight of Components A and B) of a blockcopolymer; and (B) from about 1 to about 15 wt % (based on the combinedweight of Components A and B) of one or more amine-functionalizedmodifiers selected from the group consisting of amino acids,aminotriazines, dicyandiamides and polyamines and any and allcombinations thereof.
 14. The golf ball according to claim 6 where themodified resin is made by a method comprising reacting: (A) from about90 to about 98.5 wt % (based on combined weight of Components A and B)of a block copolymer comprising (a) a first polymer block having anaromatic vinyl compound, and (b) a second polymer block having anolefinic or a conjugated diene compound, or any combination thereof; with (B) from about 1.5 to about 10 wt (based on the combined weight ofComponents A and B) of one or more amine-functionalized modifiersselected from the group consisting of 1) a compound having the generalformula(R₂N)_(m)—R′—(X(O)—(OR)_(y))_(m)—,  where R is hydrogen, or a C₁-C₂₀aliphatic, cycloaliphatic or aromatic group; R′ is a bridging groupcomprising one or more C₁-C₂₀ straight chain or branched aliphatic oralicyclic groups, or C₁-C₂₀ substituted straight chain or branchedaliphatic or alicyclic groups, or C₁-C₂₀ aromatic groups, or an oligomerof up to 12 repeating units, and X is C or S or P with the proviso thatwhen X=C, n=1 and y=1 and when X=S, n=2 and y=1, and when X=P, n=0-1 andy=2 or 4, and m=1-3, 2) an aminotriazene having the general formula

where R₁-R₅ are independently aliphatic, substituted aliphatic, alkoxy,amine, aryl, substituted aryl, heteroaryl, substituted heteroarylgroups, hydrogen or halogen; 3) a dicyandiamide having the generalformula

where R and R′ independently are hydrogen, or a C₁-C₂₀ aliphatic,cycloaliphatic or aromatic moiety or substituted aliphatic,cycloaliphatic or aromatic moiety, R is H, —CH₃, —C₂H₅, —C₆H₅, —CH₂X,—C₂H₄X, —C₆H₄X, —CH₂C₆H₄X, —CH₂CH₂C₆H₄X, or any and all combinationsthereof, and where X is hydrogen, a methyl group, an ethyl group, amethoxy group, an ethoxy group, an amino group and a dimethylaminogroup; 4) a polyamine; and 5) any and all combinations thereof.
 15. Thegolf ball according to claim 6 where the amine-functionalized modifieris selected from 4,4′-methylene-bis-(cyclohexylamine)carbamate,11-aminoundecanoicacid, 12-aminododecanoic acid, epsilon-caprolactam;omega-caprolactam, guanamine, 6-methyl-1,3,5-triazine-2,4-diamine(acetoguanamine), 6-nonyl-1,3,5-triazine-2,4-diamine (nonylguanamine),6-phenyl-1,3,5-triazine-2,4-diamine (benzoguanamine),2,4,6-triamino-triazine (melamine), dicyandiamide,N-benzyldicyandiamide, N-(4-methylbenzyl)dicyandiamide,N-(4-methoxybenzyl)dicyandiamide, N-phenethyldicyandiamide;N-(4-methylphenethyl)dicyandiamide; N-(4-methoxyphenethyl)dicyandiamide,and any and all combinations thereof.
 16. The golf ball according toclaim 6 wherein: the block copolymer is selected from the groupconsisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene(SIS), styrene-ethylene-butylene-styrene, (SEBS),styrene-ethylene/propylene-styrene (SEPS), a hydrogenated hydroxylfunctionalized styrene-isoprene-styrene, and any combination thereof;and the amine-functionalized modifier is selected from the groupconsisting of 11-aminoundecanoicacid, 12-aminododecanoic guanamine,dicyandiamide, and any and all combinations thereof.
 17. The golf ballaccording to claim 6 wherein the modified resin further comprises one ormore additional polymers selected from the group consisting ofethylene/(meth)acrylic acid copolymers, ethylene/(meth)acrylicacid/alkyl(meth)acrylate terpolymers, ethylene maleic anhydridecopolymers and terpolymers, propylene maleic anhydride copolymers andterpolymers, a unimodal ionomer, a bimodal ionomer, a modified unimodalionomer, a modified bimodal ionomer, or any and all combinationsthereof; and wherein the blend composition has a melt index of greaterthan about 3 g/10 min, a flexural modulus of from about 500 to about100,000 psi, and a material Shore D hardness of from about 25 to about70.
 18. The golf ball according to claim 6 wherein at least one of thecore, intermediate layers and outer cover layer comprises apolyalkenamer rubber selected from the group consisting of polybutenamerrubber, polypentenamer rubber, polyhexenamer rubber, polyheptenamerrubber, polyoctenamer rubber, polynonenamer rubber, polydecenamer rubberpolyundecenamer rubber, polydodecenamer rubber, polytridecenamer rubber,and any and all combinations thereof.